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Organometallics XXXX, XXX, 000000

DOI: 10.1021/om100106e

NMR Chemical Shifts of Trace Impurities: Common


Laboratory Solvents, Organics, and Gases in Deuterated
Solvents Relevant to the Organometallic
Chemist
Gregory R. Fulmer,*, Alexander J. M. Miller, Nathaniel H. Sherden,
Hugo E. Gottlieb, Abraham Nudelman, Brian M. Stoltz, John E. Bercaw, and
Karen I. Goldberg

Department of Chemistry, University of Washington, Box 351700, Seattle, Washington 98195-1700,


Arnold and Mabel Beckman Laboratories of Chemical Synthesis and Caltech Center for Catalysis and
Chemical Synthesis, Division of Chemistry and Chemical Engineering, California Institute of
Technology, Pasadena, California 91125, and Department of Chemistry, Bar Ilan University,
Ramat Gan 52900, Israel

Received February 11, 2010

Tables of 1H and 13C NMR chemical shifts have been compiled for common organic compounds
often used as reagents or found as products or contaminants in deuterated organic solvents. Building
upon the work of Gottlieb, Kotlyar, and Nudelman in the Journal of Organic Chemistry, signals for
common impurities are now reported in additional NMR solvents (tetrahydrofuran-d8, toluene-d8,
dichloromethane-d2, chlorobenzene-d5, and 2,2,2-trifluoroethanol-d3) which are frequently used in
organometallic laboratories. Chemical shifts for other organics which are often used as reagents or
internal standards or are found as products in organometallic chemistry are also reported for all the
listed solvents.

Hanging above the desk of most every chemist whose work


relies heavily on using NMR spectroscopy1 is NMR Chemical Shifts of Common Laboratory Solvents as Trace Impurities by Gottlieb, Kotlyar, and Nudelman.2 By compiling
the chemical shifts of a large number of contaminants
commonly encountered in synthetic chemistry, the publication has become an essential reference, allowing for easy
identification of known impurities in a variety of deuterated organic solvents. However, despite the utility of
Gottlieb et al.s work,3 the chemical shifts of impurities in
a number of NMR solvents often used by organometallic
chemists were not included. Tetrahydrofuran-d8 (THF-d8),
toluene-d8, dichloromethane-d2 (CD2Cl2), chlorobenzene-d5
(C6D5Cl), and 2,2,2-trifluoroethanol-d3 (TFE-d3) are commonplace in laboratories practicing inorganic syntheses.
Therefore, we have expanded the spectral data compilation
with the inclusion of chemical shifts of common impurities
recorded in the deuterated solvents heavily employed
in our organometallic laboratories. The chemical shifts
of various gases (hydrogen, methane, ethane, propane,
*To whom correspondence should be addressed. E-mail: fulmerg@
u.washington.edu.
(1) For general information on 1H and 13C{1H} NMR spectroscopy,
see: Balc, M. Basic 1H- and 13C-NMR Spectroscopy; Elsevier: Amsterdam,
2005.
(2) Gottlieb, H. E.; Kotlyar, V.; Nudelman, A. J. Org. Chem. 1997,
62, 7512.
(3) According to ACS Publications as of December 2009 (http://pubs.
acs.org/), Gottlieb et al.s publication2 is the most downloaded Journal
of Organic Chemistry article over the preceding 12 months.
r XXXX American Chemical Society

ethylene, propylene, and carbon dioxide) often encountered as reagents or products in organometallic reactions,
along with organic compounds relevant to organometallic
chemists (allyl acetate, benzaldehyde, carbon disulfide,
carbon tetrachloride, 18-crown-6, cyclohexanone, diallyl
carbonate, dimethyl carbonate, dimethyl malonate, furan,
Apiezon H grease, hexamethylbenzene, hexamethyldisiloxane, imidazole, pyrrole, and pyrrolidine), have also
been added to this expanded list.

Experimental Section
All deuterated solvents were obtained commercially through
Cambridge Isotope Laboratories, Inc. NMR spectra were
recorded at 298 K using 300, 500, or 600 MHz spectrometers
(13C{1H} NMR frequencies of 75.5, 126, or 151 MHz, respectively). Adopting the previously reported strategy,2 standard
solutions of mixtures of specific impurities were used to reduce
the number of necessary individual NMR experiments. The
combinations of organic compounds were chosen in a way in
which intermolecular interactions and resonance convolution
would be minimized. Unless otherwise stated, the standard
solutions were prepared with qualitatively equal molar amounts
of the following compounds: (solution 1) acetone, dimethylformamide, ethanol, toluene; (solution 2) benzene, dimethyl sulfoxide, ethyl acetate, methanol; (solution 3) acetic acid, chloroform, diethyl ether, 2-propanol, tetrahydrofuran; (solution 4)
acetonitrile, dichloromethane, 1,4-dioxane, n-hexane, hexamethylphosphoramide (HMPA); (solution 5) 1,2-dichloroethane,
n-pentane, pyridine, hexamethylbenzene; (solution 6) tert-butyl
alcohol, 2,6-di-tert-butyl-4-methylphenol (BHT), cyclohexane,
pubs.acs.org/Organometallics

Organometallics, Vol. XXX, No. XX, XXXX

Fulmer et al.
Table 1. 1H NMR Dataa

proton
solvent residual
signals

mult

THF-d8

CD2Cl2

CDCl3

toluene-d8

C6D6

1.72
3.58

5.32

7.26

2.08
6.97
7.01
7.09

7.16

C6D5Cl (CD3)2CO (CD3)2SO CD3CN


6.96
6.99
7.14

2.05

2.50

1.94

TFE-d3
5.02
3.88

CD3OD D2O
3.31

4.79

OH
s
2.46
1.52
1.56
0.43
0.40
1.03
2.84b
3.33b
2.13
3.66
4.87
CH3
s
1.89
2.06
2.10
1.57
1.52
1.76
1.96
1.91
1.96
2.06
1.99
2.08
s
2.05
2.12
2.17
1.57
1.55
1.77
2.09
2.09
2.08
2.19
2.15
2.22
CH3
s
1.95
1.97
2.10
0.69
0.58
1.21
2.05
2.07
1.96
1.95
2.03
2.06
CH3
CH
s
7.31
7.35
7.36
7.12
7.15
7.20
7.36
7.37
7.37
7.36
7.33
s
1.15
1.24
1.28
1.03
1.05
1.12
1.18
1.11
1.16
1.28
1.40
1.24
CH3
OH
sc
3.16
0.58
0.63
1.30
4.19
2.18
2.20
chloroform
CH
s
7.89
7.32
7.26
6.10
6.15
6.74
8.02
8.32
7.58
7.33
7.90
18-crown-6
CH2
s
3.57
3.59
3.67
3.36
3.39
3.41
3.59
3.51
3.51
3.64
3.64
3.80
s
1.44
1.44
1.43
1.40
1.40
1.37
1.43
1.40
1.44
1.47
1.45
cyclohexane
CH2
1,2-dichloroethane
CH2
s
3.77
3.76
3.73
2.91
2.90
3.26
3.87
3.90
3.81
3.71
3.78
s
5.51
5.33
5.30
4.32
4.27
4.77
5.63
5.76
5.44
5.24
5.49
dichloromethane
CH2
diethyl ether
CH3
t, 7
1.12
1.15
1.21
1.10
1.11
1.10
1.11
1.09
1.12
1.20
1.18
1.17
CH2
q, 7
3.38
3.43
3.48
3.25
3.26
3.31
3.41
3.38
3.42
3.58
3.49
3.56
m
3.43
3.57
3.65
3.43
3.46
3.49
3.56
3.51
3.53
3.67
3.61
3.67
diglyme
CH2
CH2
m
3.53
3.50
3.57
3.31
3.34
3.37
3.47
3.38
3.45
3.62
3.58
3.61
s
3.28
3.33
3.39
3.12
3.11
3.16
3.28
3.24
3.29
3.41
3.35
3.37
OCH3
dimethylformamide
CH
s
7.91
7.96
8.02
7.57
7.63
7.73
7.96
7.95
7.92
7.86
7.97
7.92
CH3
s
2.88
2.91
2.96
2.37
2.36
2.51
2.94
2.89
2.89
2.98
2.99
3.01
CH3
s
2.76
2.82
2.88
1.96
1.86
2.30
2.78
2.73
2.77
2.88
2.86
2.85
s
3.56
3.65
3.71
3.33
3.35
3.45
3.59
3.57
3.60
3.76
3.66
3.75
1,4-dioxane
CH2
DME
CH3
s
3.28
3.34
3.40
3.12
3.12
3.17
3.28
3.24
3.28
3.40
3.35
3.37
CH2
s
3.43
3.49
3.55
3.31
3.33
3.37
3.46
3.43
3.45
3.61
3.52
3.60
s
0.85
0.85
0.87
0.81
0.80
0.79
0.83
0.82
0.85
0.85
0.85
0.82
ethane
CH3
ethanol
CH3
t, 7
1.10
1.19
1.25
0.97
0.96
1.06
1.12
1.06
1.12
1.22
1.19
1.17
d
q, 7
3.51
3.66
3.72
3.36
3.34
3.51
3.57
3.44
3.54
3.71
3.60
3.65
CH2
c,d
OH
s
3.30
1.33
1.32
0.83
0.50
1.39
3.39
4.63
2.47
s
1.94
2.00
2.05
1.69
1.65
1.78
1.97
1.99
1.97
2.03
2.01
2.07
ethyl acetate
CH3CO
CH2CH3
q, 7
4.04
4.08
4.12
3.87
3.89
3.96
4.05
4.03
4.06
4.14
4.09
4.14
CH2CH3
t, 7
1.19
1.23
1.26
0.94
0.92
1.04
1.20
1.17
1.20
1.26
1.24
1.24
s
5.36
5.40
5.40
5.25
5.25
5.29
5.38
5.41
5.41
5.40
5.39
5.44
ethylene
CH2
e
ethylene glycol
CH2
s
3.48
3.66
3.76
3.36
3.41
3.58
3.28
3.34
3.51
3.72
3.59
3.65
CH3
m
0.85-0.91 0.84-0.90 0.84-0.87 0.89-0.96 0.90-0.98 0.86-0.92
0.90
0.82-0.88
0.88-0.94 0.86-0.93
H greasef
CH2
br s
1.29
1.27
1.25
1.33
1.32
1.30
1.29
1.24
1.33
1.29
s
2.18
2.20
2.24
2.10
2.13
2.10
2.17
2.14
2.19
2.24
2.19
hexamethylbenzene
CH3
n-hexane
CH3
t, 7
0.89
0.89
0.88
0.88
0.89
0.85
0.88
0.86
0.89
0.91
0.90
CH2
m
1.29
1.27
1.26
1.22
1.24
1.19
1.28
1.25
1.28
1.31
1.29
s
0.07
0.07
0.07
0.10
0.12
0.10
0.07
0.06
0.07
0.08
0.07
0.28
HMDSO
CH3
HMPA
CH3
d,9.5
2.58
2.60
2.65
2.42
2.40
2.47
2.59
2.53
2.57
2.63
2.64
2.61
s
4.55
4.59
4.62
4.50
4.47
4.49
4.54
4.61
4.57
4.53
4.56
hydrogen
H2
imidazole
CH(2)
s
7.48
7.63
7.67
7.30
7.33
7.53
7.62
7.63
7.57
7.61
7.67
7.78
CH(4,5)
s
6.94
7.07
7.10
6.86
6.90
7.01
7.04
7.01
7.01
7.03
7.05
7.14
methane
CH4
s
0.19
0.21
0.22
0.17
0.16
0.15
0.17
0.20
0.20
0.18
0.20
0.18
sg
3.27
3.42
3.49
3.03
3.07
3.25
3.31
3.16
3.28
3.44
3.34
3.34
methanol
CH3
c,g
OH
s
3.02
1.09
1.09
1.30
3.12
4.01
2.16
nitromethane
CH3
s
4.31
4.31
4.33
3.01
2.94
3.59
4.43
4.42
4.31
4.28
4.34
4.40
t, 7
0.89
0.89
0.88
0.87
0.87
0.84
0.88
0.86
0.89
0.90
0.90
n-pentane
CH3
CH2
m
1.31
1.30
1.27
1.25
1.23
1.23
1.27
1.27
1.29
1.33
1.29
t, 7.3
0.90
0.90
0.90
0.89
0.86
0.84
0.88
0.87
0.90
0.90
0.91
0.88
propane
CH3
CH2
sept, 7.3
1.33
1.32
1.32
1.32
1.26
1.26
1.31
1.29
1.33
1.33
1.34
1.30
d, 6
1.08
1.17
1.22
0.95
0.95
1.04
1.10
1.04
1.09
1.20
1.50
1.17
2-propanol
CH3
CH
sept, 6
3.82
3.97
4.04
3.65
3.67
3.82
3.90
3.78
3.87
4.05
3.92
4.02
propylene
CH3
dt, 6.4, 1.5
1.69
1.71
1.73
1.55
1.55
1.58
1.68
1.68
1.70
1.70
1.70
1.70
dm, 10
4.89
4.93
4.94
4.92
4.95
4.91
4.90
4.94
4.93
4.93
4.91
4.95
CH2(1)
CH2(2)
dm, 17
4.99
5.03
5.03
4.98
5.01
4.98
5.00
5.03
5.04
5.03
5.01
5.06
CH
m
5.79
5.84
5.83
5.70
5.72
5.72
5.81
5.80
5.85
5.87
5.82
5.90
pyridine
CH(2,6)
m
8.54
8.59
8.62
8.47
8.53
8.51
8.58
8.58
8.57
8.45
8.53
8.52
CH(3,5)
m
7.25
7.28
7.29
6.67
6.66
6.90
7.35
7.39
7.33
7.40
7.44
7.45
CH(4)
m
7.65
7.68
7.68
6.99
6.98
7.25
7.76
7.79
7.73
7.82
7.85
7.87
pyrrole
NH
br t
9.96
8.69
8.40
7.71
7.80
8.61
10.02
10.75
9.27
CH(2,5)
m
6.66
6.79
6.83
6.43
6.48
6.62
6.77
6.73
6.75
6.84
6.72
6.93
CH(3,4)
m
6.02
6.19
6.26
6.27
6.37
6.27
6.07
6.01
6.10
6.24
6.08
6.26
h
pyrrolidine
CH2(2,5)
m
2.75
2.82
2.87
2.54
2.54
2.64
2.67
2.75
3.11
2.80
3.07
CH2(3,4)
m
1.59
1.67
1.68
1.36
1.33
1.43
1.55
1.61
1.93
1.72
1.87
s
0.11
0.09
0.07
0.26
0.29
0.14
0.13
-0.06
0.08
0.16
0.10
silicone grease
CH3
tetrahydrofuran
CH2(2,5)
m
3.62
3.69
3.76
3.54
3.57
3.59
3.63
3.60
3.64
3.78
3.71
3.74
m
1.79
1.82
1.85
1.43
1.40
1.55
1.79
1.76
1.80
1.91
1.87
1.88
CH2(3,4)
toluene
CH3
s
2.31
2.34
2.36
2.11
2.11
2.16
2.32
2.30
2.33
2.33
2.32
CH(2,4,6)
m
7.10
7.15
7.17
6.96-7.01
7.02
7.01-7.08 7.10-7.20
7.18
7.10-7.30 7.10-7.30
7.16
CH(3,5)
m
7.19
7.24
7.25
7.09
7.13
7.10-7.17 7.10-7.20
7.25
7.10-7.30 7.10-7.30
7.16
triethylamine
CH3
t, 7
0.97
0.99
1.03
0.95
0.96
0.93
0.96
0.93
0.96
1.31
1.05
0.99
q,7
2.46
2.48
2.53
2.39
2.40
2.39
2.45
2.43
2.45
3.12
2.58
2.57
CH2
water
acetic acid
acetone
acetonitrile
benzene
tert -butyl alcohol

a
Except for the compounds in solutions 8-10, as well as the gas samples, hexamethylbenzene, and the corrected values mentioned in the Supporting
Information, all data for the solvents CDCl3, C6D6, (CD3)2CO, (CD3)2SO, CD3CN, CD3OD, and D2O were previously reported in ref 2. b A signal for
HDO is also observed in (CD3)2SO (3.30 ppm) and (CD3)2CO (2.81 ppm), often seen as a 1:1:1 triplet (2JH,D = 1 Hz). c Not all OH signals were
observable. d In some solvents, the coupling interaction between the CH2 and the OH protons may be observed (J = 5 Hz). e In CD3CN, the OH proton
was seen as a multiplet at 2.69 ppm, as well as extra coupling to the CH2 resonance. f Apiezon brand H grease. g In some solvents, a coupling interaction
between the CH3 and the OH protons may be observed (J = 5.5 Hz). h Pyrrolidine was observed to react with (CD3)2CO.

Article

Organometallics, Vol. XXX, No. XX, XXXX

Table 2. 13C{1H} NMR Dataa


carbon
solvent signals

acetic acid
acetone
acetonitrile
benzene
tert -butyl alcohol
carbon dioxide
carbon disulfide
carbon tetrachloride
chloroform
18-crown-6
cyclohexane
1,2-dichloroethane
dichloromethane
diethyl ether
diglyme
dimethylformamide
1,4-dioxane
DME
ethane
ethanol
ethyl acetate

ethylene
ethylene glycol
H greaseb
hexamethylbenzene
n-hexane
HMDSO
HMPAc
imidazole
methane
methanol
nitromethane
n-pentane
propane
2-propanol
propylene
pyridine
pyrrole
pyrrolidinee
silicone grease
tetrahydrofuran
toluene

triethylamine

CO
CH3
CO
CH3
CN
CH3
CH
(CH3)3C
(CH3)3C
CO2
CS2
CCl4
CH
CH2
CH2
CH2
CH2
CH3
CH2
CH3
CH2
CH2
CH
CH3
CH3
CH2
CH3
CH2
CH3
CH3
CH2
CH3CO
CO
CH2
CH3
CH2
CH2
CH2
C
CH3
CH3
CH2(2,5)
CH2(3,4)
CH3
CH3
CH(2)
CH(4,5)
CH4
CH3
CH3
CH3
CH2(2,4)
CH2(3)
CH3
CH2
CH3
CH
CH3
CH2
CH
CH(2,6)
CH(3,5)
CH(4)
CH(2,5)
CH(3,4)
CH2(2,5)
CH2(3,4)
CH3
CH2(2,5)
CH2(3,4)
CH3
C(1)
CH(2,6)
CH(3,5)
CH(4)
CH3
CH2

THF-d8

CD2Cl2

CDCl3

toluene- d8

C6D6

C6D5Cl

(CD3)2CO

(CD3)2SO

CD3CN

TFE-d3

CD3OD

67.21
25.31

53.84

77.16

137.48
128.87
127.96
125.13
20.43

128.06

134.19
129.26
128.25
125.96

29.84
206.26

39.52

1.32
118.26

61.50
126.28

49.00

171.69
20.13
204.19
30.17
116.79
0.45
128.84
67.50
30.57
125.69
193.37
96.89
79.24
71.34
27.58
44.64
54.67
15.49
66.14
58.72
71.17
72.72
161.96
35.65
30.70
67.65
58.72
72.58
6.79
18.90
57.60
20.45
170.32
60.30
14.37
123.09
64.35
30.45
131.88
16.71
14.22
23.33
32.34
1.83
36.89
135.72
122.20
-4.90
49.64
62.49
14.18
23.00
34.87
16.60
16.82
25.70
66.14
19.27
115.74
134.02
150.57
124.08
135.99
118.03
107.74
45.82
26.17
1.20
68.03
26.19
21.29
138.24
129.47
128.71
125.84
12.51
47.18

175.85
20.91
206.78
31.00
116.92
2.03
128.68
69.11
31.46
125.26
192.95
96.52
77.99
70.47
27.38
44.35
54.24
15.44
66.11
58.95
70.70
72.25
162.57
36.56
31.39
67.47
59.02
72.24
6.91
18.69
58.57
21.15
171.24
60.63
14.37
123.20
64.08
30.14
132.09
16.93
14.28
23.07
32.01
1.96
36.99
135.76
122.16
-4.33
50.45
63.03
14.24
22.77
34.57
16.63
16.63
25.43
64.67
19.47
115.70
134.21
150.27
124.06
136.16
117.93
108.02
47.02
25.83
1.22
68.16
25.98
21.53
138.36
129.35
128.54
125.62
12.12
46.75

175.99
20.81
207.07
30.92
116.43
1.89
128.37
69.15
31.25
124.99
192.83
96.34
77.36
70.55
26.94
43.50
53.52
15.20
65.91
59.01
70.51
71.90
162.62
36.50
31.45
67.14
59.08
71.84
6.89
18.41
58.28
21.04
171.36
60.49
14.19
123.13
63.79
29.71
132.21
16.98
14.14
22.70
31.64
1.97
36.87
135.38
122.00
-4.63
50.41
62.50
14.08
22.38
34.16
16.63
16.37
25.14
64.50
19.50
115.74
133.91
149.90
123.75
135.96
117.77
107.98
46.93
25.56
1.19
67.97
25.62
21.46
137.89
129.07
128.26
125.33
11.61
46.25

175.30
20.27
204.00
30.03
115.76
0.03
128.57
68.12
30.49
124.86
192.71
96.57
77.89
70.86
27.31
43.40
53.47
15.47
65.94
58.62
70.92
72.39
161.93
35.22
30.64
67.17
58.63
72.25
6.94
18.78
57.81
20.46
170.02
60.08
14.23
122.92
64.29
30.31
131.72
16.84
14.34
23.12
32.06
1.99
36.80
135.57
122.13
-4.34
49.90
61.14
14.27
22.79
34.54
16.65
16.63
25.24
64.12
19.32
115.89
133.61
150.25
123.46
135.17
117.61
108.15
47.12
25.75
1.37
67.75
25.79
21.37
137.84
129.33
128.51
125.66
12.39
46.82

175.82
20.37
204.43
30.14
116.02
0.20
128.62
68.19
30.47
124.76
192.69
96.44
77.79
70.59
27.23
43.59
53.46
15.46
65.94
58.66
70.87
72.35
162.13
35.25
30.72
67.16
58.68
72.21
6.96
18.72
57.86
20.56
170.44
60.21
14.19
122.96
64.34
30.22
131.79
16.95
14.32
23.04
31.96
2.05
36.88
135.76
122.16
-4.29
49.97
61.16
14.25
22.72
34.45
16.66
16.60
25.18
64.23
19.38
115.92
133.69
150.27
123.58
135.28
117.78
108.21
46.86
25.65
1.38
67.80
25.72
21.10
137.91
129.33
128.56
125.68
12.35
46.77

175.67
20.40
204.83
30.12
115.93
0.63
128.38
68.19
31.13
126.08
192.49
96.38
77.67
70.55
26.99
43.60
53.54
15.35
65.79
58.42
70.56
72.07
162.01
35.45
30.71
66.95
58.31
71.81
6.91
18.55
57.63
20.50
170.20
60.06
14.07
122.95
64.03
30.11
131.54
16.68
14.18
22.86
31.77
1.92
36.64
135.50
121.96
-4.33
49.66
61.68
14.10
22.54
34.26
16.56
16.48
25.14
64.18
19.32
115.86
133.57
149.93
123.49
135.32
117.65
108.03
46.75
25.59
1.09
67.64
25.68
21.23
137.65
129.12
128.31
125.43
11.87
46.36

172.31
20.51
205.87
30.60
117.60
1.12
129.15
68.13
30.72
125.81
193.58
96.65
79.19
71.25
27.51
45.25
54.95
15.78
66.12
58.77
71.03
72.63
162.79
36.15
31.03
67.60
58.45
72.47
6.88
18.89
57.72
20.83
170.96
60.56
14.50
123.47
64.26

171.93
20.95
206.31
30.56
117.91
1.03
128.30
66.88
30.38
124.21
192.63
95.44
79.16
69.85
26.33
45.02
54.84
15.12
62.05
57.98
69.54
71.25
162.29
35.73
30.73
66.36
58.03
71.17
6.61
18.51
56.07
20.68
170.31
59.74
14.40
123.52
62.76

173.21
20.73
207.43
30.91
118.26
1.79
129.32
68.74
30.68
125.89
193.60
96.68
79.17
71.22
27.63
45.54
55.32
15.63
66.32
58.90
70.99
72.63
163.31
36.57
31.32
67.72
58.89
72.47
6.99
18.80
57.96
21.16
171.68
60.98
14.54
123.69
64.22

177.96
20.91
32.35
214.98
118.95
1.00
129.84
72.35
31.07
126.92
196.26
97.74
78.83
70.80
28.34
45.28
54.46
15.33
67.55
59.40
73.05
71.33
166.01
37.76
30.96
68.52
59.52
72.87
7.01
18.11
59.68
21.18
175.55
62.70
14.36
124.08
64.87

175.11
20.56
209.67
30.67
118.06
0.85
129.34
69.40
30.91
126.31
193.82
97.21
79.44
71.47
27.96
45.11
54.78
15.46
66.88
59.06
71.33
72.92
164.73
36.89
31.61
68.11
59.06
72.72
6.98
18.40
58.26
20.88
172.89
61.50
14.49
123.46
64.30

132.22
16.86
14.34
23.28
32.30
2.01
37.04
135.89
122.31
-5.33
49.77
63.21
14.29
22.98
34.83
16.68
16.78
25.67
63.85
19.42
116.03
134.34
150.67
124.57
136.56
117.98
108.04

131.10
16.60
13.88
22.05
30.95
1.96
36.42
135.15
121.55
-4.01
48.59
63.28
13.28
21.70
33.48
16.34
15.67
25.43
64.92
19.20
116.07
133.55
149.58
123.84
136.05
117.32
107.07
46.51
25.26

132.61
16.94
14.43
23.40
32.36
2.07
37.10
136.33
122.78
-4.61
49.90
63.66
14.37
23.08
34.89
16.73
16.91
25.55
64.30
19.48
116.12
134.78
150.76
127.76
136.89
118.47
108.31
47.57
26.34

67.03
25.14
20.99
137.35
128.88
128.18
125.29
11.74
45.74

68.33
26.27
21.50
138.90
129.94
129.23
126.28
12.38
47.10

134.04
17.04
14.63
24.06
33.17
2.09
37.21
136.58
122.93
-5.88
50.67
63.17
14.54
23.75
35.76
16.93
17.46
25.21
66.69
19.63
116.38
136.00
149.76
126.27
139.62
119.61
108.85
47.43
25.73
2.87
69.53
26.69
21.62
139.92
130.58
129.79
126.82
9.51
48.45

132.53
16.90
14.45
23.68
32.73
1.99
37.00
136.31
122.60
-4.90
49.86
63.08
14.39
23.38
35.30
16.80
17.19
25.27
64.71
19.50
116.04
134.61
150.07
125.53
138.35
118.28
108.11
47.23
26.29
2.10
68.83
26.48
21.50
138.85
129.91
129.20
126.29
11.09
46.96

1.40
68.07
26.15
21.46
138.48
129.76
129.03
126.12
12.49
47.07

D2O

177.21
21.03
215.94
30.89
119.68
1.47
70.36
30.29
197.25
96.73
70.14

14.77
66.42
58.67
70.05
71.63
165.53
37.54
32.03
67.19
58.67
71.49
17.47
58.05
21.15
175.26
62.32
13.92
63.17

2.31
36.46
136.65
122.43
49.50d
63.22

24.38
64.88

149.18
125.12
138.27
119.06
107.83
46.83
25.86
68.68
25.67

9.07
47.19

a
Except for the compounds in solutions 8-10, as well as the gas samples, hexamethylbenzene, and the corrected values mentioned in the Supporting
Information, all data for the solvents CDCl3, C6D6, (CD3)2CO, (CD3)2SO, CD3CN, CD3OD, and D2O were previously reported in ref 2. b Apiezon
brand H grease. c Phosphorus coupling was observed (2JPC = 3 Hz). d Internal reference; see text. e Pyrrolidine was observed to react with (CD3)2CO.

Organometallics, Vol. XXX, No. XX, XXXX

1,2-dimethoxyethane (DME), nitromethane, poly(dimethylsiloxane)


(silicone grease), triethylamine; (solution 7) diglyme, dimethylacetamide, ethylene glycol, ethyl methyl ketone; (solution 8)
allyl acetate, 2,6-di-tert-butyl-4-methoxyphenol (BHA), longchain, linear aliphatic hydrocarbons from pump oil;4 (solution 9) benzaldehyde, carbon disulfide, carbon tetrachloride,
cyclohexanone, dimethyl malonate, furan, Apiezon H grease
(H grease); (solution 10) 18-crown-6, diallyl carbonate, dimethyl
carbonate, hexamethyldisiloxane (HMDSO), imidazole, pyrrole,
pyrrolidine.5 In the case of TFE-d3, nitromethane was omitted
from solution 6 and run separately, since the protons of nitromethane exchange with deuterium from TFE-d3 in the presence
of triethylamine. In the case of (CD3)2CO, pyrrolidine was
omitted from solution 10, since the two compounds were observed
to react with each other. The gases used in this study included
hydrogen, methane, ethane, propane, ethylene, propylene, and
carbon dioxide.
Before examining the various standard contaminant solutions by 1H NMR spectroscopy, solvent residual signals6 and
chemical shifts for H2O7 for each NMR solvent were referenced against tetramethylsilane (TMS, 0 ppm) and reported.
Before collecting 13C{1H} NMR spectral data, solvent signals6
were recorded with reference to the signal of a TMS internal
standard. For D2O, 1H NMR spectra were referenced to the
methyl signal ( 0 ppm) of sodium 3-(trimethylsilyl)propanesulfonate,8,9 and 13C{1H} NMR spectra were referenced to the
signal for the methyl group of methanol (one drop, added as an
internal standard), which was set to 49.50 ppm.2
In a typical experiment for collecting 1H NMR spectral data, a
3 L sample of a standard contaminant solution was added to
an NMR tube containing approximately 0.4 mL of a deuterated
solvent. For 13C{1H} NMR spectral data collection, an approximately 50 L sample of the standard contaminant solution was
added. When there was any uncertainty in the assignment of a
resonance, the solution was spiked with an additional 1-2 L
of the impurity in question to accurately identify its chemical
shift. In cases where the chemical shifts of resonances were
highly dependent on the concentration of the impurities present, ambiguous resonances were instead resolved via gradient(4) VWR brand vacuum pump oil #19.
(5) The components of solution 10 were stable together in dilute
solution but unstable when neat mixtures were prepared. In general, it
was observed that the nitrogen-containing compounds and possibly
18-crown-6 catalyzed the hydrolysis of the carbonates, reacted directly
with them, or both. Therefore, for the purpose of storage, the solution
was partitioned into two subsolutions: (solution 10A) 18-crown-6,
imidazole, pyrrole, pyrrolidine; (solution 10B) diallyl carbonate, dimethyl carbonate, hexamethyldisiloxane. These subsolutions were
stable for long periods as neat mixtures and were combined to form
solution 10 by adding equal portions to an NMR tube containing the
desired deuterated solvent.
(6) For 1H NMR spectra, the solvent residual signals arise from the
proton of isotopomers containing one less deuterium atom than the
perdeuterated solvent: e.g., CDHCl2 in CD2Cl2. For 13C NMR spectra,
the solvent signals arise from the 13C atoms at natural abundance in the
perdeuterated solvent.
(7) The chemical shift for H2O can vary depending on the temperature, [H2O], and the solutes present: e.g., a downfield shift may be
observed in the presence of any hydrogen bond acceptors. For more
information see page 75 of ref 1.
(8) Harris, R. K.; Becker, E. D.; Cabral de Menezes, S. M.; Granger,
P.; Hoffman, R. E.; Zilm, K. W. Pure Appl. Chem. 2008, 80, 59.
(9) For information on the temperature dependence of HDO chemical shifts in D2O, see ref 2.

Fulmer et al.
selected heteronuclear single-quantum coherence (gs-HSQC)
and gradient-selected heteronuclear multiple-quantum coherence
(gs-HMQC) NMR spectroscopies. For the experiments involving
gases, a J. Young NMR tube containing approximately 0.4 mL of
NMR solvent was first degassed with three freeze-pump-thaw
cycles. Using a vacuum line equipped with a gas manifold, 1 atm
of the desired gas was added to the tube. Each gas was run
separately, degassing between each gas sample.

Results and Discussion


Chemical shifts for each of the impurities are reported in
the tables: 1H and 13C{1H} NMR spectral data of all substrates are presented in Tables 1 and 2, respectively. Notably,
physically larger tables, containing all the data from Tables 1
and 2 as well as the chemical shifts of additional organic
compounds, are provided in the Supporting Information.
Unless noted otherwise, coupling constants (reported in Hz)
and resonance multiplicities (abbreviated as follows: s =
singlet, d = doublet, t = triplet, q = quartet, p = pentet,
sept = septet, m = multiplet, br = broad) were observed to
be solvent-independent.
It was noted that the amount of gas dissolved in solution
gave 1H NMR signal integrations that were qualitatively
comparable to those for the solutions made with the 3 L
additions of the liquid or solid contaminants. However, typically in order to observe signals for the gas samples by 13C{1H}
NMR spectroscopy, additional time for data collection was
required. The solubility of each gas in D2O was extremely
limited, making 13C detection impractical. Of all the gases,
methane required the most number of transients in order to
obtain an observable signal by 13C{1H} NMR spectroscopy.
In most cases, the 13C chemical shift of methane was acquired
through the use of gs-HMQC NMR spectroscopy to provide
enhanced sensitivity. In order to reflect what would be observed in typical NMR-scale experiments, 13C detection was
not pursued with isotopically enriched gases. A number of
misreported values were discovered in the years since the
original publication10 and in the preparation of this paper.
These are detailed in the Supporting Information, and the
values are now correctly listed in Tables 1 and 2.

Acknowledgment. G.R.F. and K.I.G. thank the Department of Energy (Contract No. DE-FG02-06ER15765) for
support. A.J.M.M. and J.E.B. thank the Moore Foundation for support. N.H.S. and B.M.S. thank Abbott Laboratories, Amgen, Merck, Bristol-Myers Squibb, Boehringer
Ingelheim, the Gordon and Betty Moore Foundation, and
Caltech for financial support.
Supporting Information Available: Large-format tables of the
all the NMR data. This material is available free of charge via
the Internet at http://pubs.acs.org.
(10) The misreported value for acetonitrile in C6D6 from the original
paper2 was also pointed out by Dr. Jongwook Choi, to whom we are
grateful.

7512

J. Org. Chem. 1997, 62, 7512-7515

NMR Chemical Shifts of Common


Laboratory Solvents as Trace Impurities
Hugo E. Gottlieb,* Vadim Kotlyar, and
Abraham Nudelman*
Department of Chemistry, Bar-Ilan University,
Ramat-Gan 52900, Israel
Received June 27, 1997

In the course of the routine use of NMR as an aid for


organic chemistry, a day-to-day problem is the identification of signals deriving from common contaminants
(water, solvents, stabilizers, oils) in less-than-analytically-pure samples. This data may be available in the
literature, but the time involved in searching for it may
be considerable. Another issue is the concentration
dependence of chemical shifts (especially 1H); results
obtained two or three decades ago usually refer to much
more concentrated samples, and run at lower magnetic
fields, than todays practice.
We therefore decided to collect 1H and 13C chemical
shifts of what are, in our experience, the most popular
extra peaks in a variety of commonly used NMR
solvents, in the hope that this will be of assistance to
the practicing chemist.
Experimental Section
NMR spectra were taken in a Bruker DPX-300 instrument
(300.1 and 75.5 MHz for 1H and 13C, respectively). Unless
otherwise indicated, all were run at room temperature (24 ( 1
C). For the experiments in the last section of this paper, probe
temperatures were measured with a calibrated Eurotherm 840/T
digital thermometer, connected to a thermocouple which was
introduced into an NMR tube filled with mineral oil to approximately the same level as a typical sample. At each
temperature, the D2O samples were left to equilibrate for at least
10 min before the data were collected.
In order to avoid having to obtain hundreds of spectra, we
prepared seven stock solutions containing approximately equal
amounts of several of our entries, chosen in such a way as to
prevent intermolecular interactions and possible ambiguities in
assignment. Solution 1: acetone, tert-butyl methyl ether, dimethylformamide, ethanol, toluene. Solution 2: benzene, dimethyl sulfoxide, ethyl acetate, methanol. Solution 3: acetic
acid, chloroform, diethyl ether, 2-propanol, tetrahydrofuran.
Solution 4: acetonitrile, dichloromethane, dioxane, n-hexane,
HMPA. Solution 5: 1,2-dichloroethane, ethyl methyl ketone,
n-pentane, pyridine. Solution 6: tert-butyl alcohol, BHT, cyclohexane, 1,2-dimethoxyethane, nitromethane, silicone grease,
triethylamine. Solution 7: diglyme, dimethylacetamide, ethylene glycol, grease (engine oil). For D2O. Solution 1: acetone,
tert-butyl methyl ether, dimethylformamide, ethanol, 2-propanol.
Solution 2: dimethyl sulfoxide, ethyl acetate, ethylene glycol,
methanol. Solution 3: acetonitrile, diglyme, dioxane, HMPA,
pyridine. Solution 4: 1,2-dimethoxyethane, dimethylacetamide,
ethyl methyl ketone, triethylamine. Solution 5: acetic acid, tertbutyl alcohol, diethyl ether, tetrahydrofuran. In D2O and
CD3OD nitromethane was run separately, as the protons
exchanged with deuterium in presence of triethylamine.

Results
Proton Spectra (Table 1). A sample of 0.6 mL of the
solvent, containing 1 L of TMS,1 was first run on its
own. From this spectrum we determined the chemical
shifts of the solvent residual peak2 and the water peak.
It should be noted that the latter is quite temperature(1) For recommendations on the publication of NMR data, see:
IUPAC Commission on Molecular Structure and Spectroscopy. Pure
Appl. Chem. 1972, 29, 627; 1976, 45, 217.

S0022-3263(97)01176-6 CCC: $14.00

Figure 1. Chemical shift of HDO as a function of temperature.

dependent (vide infra). Also, any potential hydrogenbond acceptor will tend to shift the water signal downfield; this is particularly true for nonpolar solvents. In
contrast, in e.g. DMSO the water is already strongly
hydrogen-bonded to the solvent, and solutes have only a
negligible effect on its chemical shift. This is also true
for D2O; the chemical shift of the residual HDO is very
temperature-dependent (vide infra) but, maybe counterintuitively, remarkably solute (and pH) independent.
We then added 3 L of one of our stock solutions to
the NMR tube. The chemical shifts were read and are
presented in Table 1. Except where indicated, the
coupling constants, and therefore the peak shapes, are
essentially solvent-independent and are presented only
once.
For D2O as a solvent, the accepted reference peak (
) 0) is the methyl signal of the sodium salt of 3-(trimethylsilyl)propanesulfonic acid; one crystal of this was added
to each NMR tube. This material has several disadvantages, however: it is not volatile, so it cannot be readily
eliminated if the sample has to be recovered. In addition,
unless one purchases it in the relatively expensive
deuterated form, it adds three more signals to the
spectrum (methylenes 1, 2, and 3 appear at 2.91, 1.76,
and 0.63 ppm, respectively). We suggest that the residual HDO peak be used as a secondary reference; we
find that if the effects of temperature are taken into
account (vide infra), this is very reproducible. For D2O,
we used a different set of stock solutions, since many of
the less polar substrates are not significantly watersoluble (see Table 1). We also ran sodium acetate and
sodium formate (chemical shifts: 1.90 and 8.44 ppm,
respectively).
Carbon Spectra (Table 2). To each tube, 50 L of
the stock solution and 3 L of TMS1 were added. The
solvent chemical shifts3 were obtained from the spectra
containing the solutes, and the ranges of chemical shifts
(2) I.e., the signal of the proton for the isotopomer with one less
deuterium than the perdeuterated material, e.g., CHCl3 in CDCl3 or
C6D5H in C6D6. Except for CHCl3, the splitting due to JHD is typically
observed (to a good approximation, it is 1/6.5 of the value of the
corresponding JHH). For CHD2 groups (deuterated acetone, DMSO,
acetonitrile), this signal is a 1:2:3:2:1 quintet with a splitting of ca. 2
Hz.
(3) In contrast to what was said in note 2, in the 13C spectra the
solvent signal is due to the perdeuterated isotopomer, and the onebond couplings to deuterium are always observable (ca. 20-30 Hz).

1997 American Chemical Society

Notes

J. Org. Chem., Vol. 62, No. 21, 1997 7513


Table 1.
proton

solvent residual peak


H2O
acetic acid
acetone
acetonitrile
benzene
tert-butyl alcohol
tert-butyl methyl ether
BHTb

chloroform
cyclohexane
1,2-dichloroethane
dichloromethane
diethyl ether
diglyme
1,2-dimethoxyethane
dimethylacetamide
dimethylformamide
dimethyl sulfoxide
dioxane
ethanol
ethyl acetate
ethyl methyl ketone
ethylene glycol
grease f
n-hexane
HMPAg
methanol
nitromethane
n-pentane
2-propanol
pyridine
silicone greasei
tetrahydrofuran
toluene
triethylamine

CH3
CH3
CH3
CH
CH3
OHc
CCH3
OCH3
ArH
OHc
ArCH3
ArC(CH3)3
CH
CH2
CH2
CH2
CH3
CH2
CH2
CH2
OCH3
CH3
CH2
CH3CO
NCH3
NCH3
CH
CH3
CH3
CH3
CH2
CH3
CH2
OH
CH3CO
CH2CH3
CH2CH3
CH3CO
CH2CH3
CH2CH3
CH
CH3
CH2
CH3
CH2
CH3
CH3
OH
CH3
CH3
CH2
CH3
CH
CH(2)
CH(3)
CH(4)
CH3
CH2
CH2O
CH3
CH(o/p)
CH(m)
CH3
CH2

mult
s
s
s
s
s
s
s
s
s
s
s
s
s
s
s
s
s
t, 7
q, 7
m
m
s
s
s
s
s
s
s
s
s
s
s
t, 7
q, 7d
sc,d
s
q, 7
t, 7
s
q, 7
t, 7
se
m
br s
t
m
d, 9.5
sh
sc,h
s
t, 7
m
d, 6
sep, 6
m
m
m
s
m
m
s
m
m
t,7
q, 7

CDCl3

1H

NMR Data

(CD3)2CO

7.26
1.56
2.10
2.17
2.10
7.36
1.28

2.05
2.84a
1.96
2.09
2.05
7.36
1.18

1.19
3.22
6.98
5.01
2.27
1.43
7.26
1.43
3.73
5.30
1.21
3.48
3.65
3.57
3.39
3.40
3.55
2.09
3.02
2.94
8.02
2.96
2.88
2.62
3.71
1.25
3.72
1.32
2.05
4.12
1.26
2.14
2.46
1.06
3.76
0.86
1.26
0.88
1.26
2.65
3.49
1.09
4.33
0.88
1.27
1.22
4.04
8.62
7.29
7.68
0.07
1.85
3.76
2.36
7.17
7.25
1.03
2.53

1.13
3.13
6.96
2.22
1.41
8.02
1.43
3.87
5.63
1.11
3.41
3.56
3.47
3.28
3.28
3.46
1.97
3.00
2.83
7.96
2.94
2.78
2.52
3.59
1.12
3.57
3.39
1.97
4.05
1.20
2.07
2.45
0.96
3.28
0.87
1.29
0.88
1.28
2.59
3.31
3.12
4.43
0.88
1.27
1.10
3.90
8.58
7.35
7.76
0.13
1.79
3.63
2.32
7.1-7.2
7.1-7.2
0.96
2.45

(CD3)2SO

C6D6

CD3CN

CD3OD

D2O

2.50
3.33a
1.91
2.09
2.07
7.37
1.11
4.19
1.11
3.08
6.87
6.65
2.18
1.36
8.32
1.40
3.90
5.76
1.09
3.38
3.51
3.38
3.24
3.24
3.43
1.96
2.94
2.78
7.95
2.89
2.73
2.54
3.57
1.06
3.44
4.63
1.99
4.03
1.17
2.07
2.43
0.91
3.34

7.16
0.40
1.55
1.55
1.55
7.15
1.05
1.55
1.07
3.04
7.05
4.79
2.24
1.38
6.15
1.40
2.90
4.27
1.11
3.26
3.46
3.34
3.11
3.12
3.33
1.60
2.57
2.05
7.63
2.36
1.86
1.68
3.35
0.96
3.34

1.94
2.13
1.96
2.08
1.96
7.37
1.16
2.18
1.14
3.13
6.97
5.20
2.22
1.39
7.58
1.44
3.81
5.44
1.12
3.42
3.53
3.45
3.29
3.28
3.45
1.97
2.96
2.83
7.92
2.89
2.77
2.50
3.60
1.12
3.54
2.47
1.97
4.06
1.20
2.06
2.43
0.96
3.51
0.86
1.27
0.89
1.28
2.57
3.28
2.16
4.31
0.89
1.29
1.09
3.87
8.57
7.33
7.73
0.08
1.80
3.64
2.33
7.1-7.3
7.1-7.3
0.96
2.45

3.31
4.87
1.99
2.15
2.03
7.33
1.40

4.79

0.86
1.25
2.53
3.16
4.01
4.42
0.86
1.27
1.04
3.78
8.58
7.39
7.79
1.76
3.60
2.30
7.18
7.25
0.93
2.43

1.65
3.89
0.92
1.58
1.81
0.85
3.41
0.92
1.36
0.89
1.24
2.40
3.07
2.94
0.87
1.23
0.95
3.67
8.53
6.66
6.98
0.29
1.40
3.57
2.11
7.02
7.13
0.96
2.40

1.15
3.20
6.92
2.21
1.40
7.90
1.45
3.78
5.49
1.18
3.49
3.61
3.58
3.35
3.35
3.52
2.07
3.31
2.92
7.97
2.99
2.86
2.65
3.66
1.19
3.60

2.08
2.22
2.06
1.24
1.21
3.22

1.17
3.56
3.67
3.61
3.37
3.37
3.60
2.08
3.06
2.90
7.92
3.01
2.85
2.71
3.75
1.17
3.65

2.01
4.09
1.24
2.12
2.50
1.01
3.59
0.88
1.29
0.90
1.29
2.64
3.34

2.07
4.14
1.24
2.19
3.18
1.26
3.65

4.34
0.90
1.29
1.50
3.92
8.53
7.44
7.85
0.10
1.87
3.71
2.32
7.16
7.16
1.05
2.58

4.40

2.61
3.34

1.17
4.02
8.52
7.45
7.87
1.88
3.74

0.99
2.57

a In these solvents the intermolecular rate of exchange is slow enough that a peak due to HDO is usually also observed; it appears at
2.81 and 3.30 ppm in acetone and DMSO, respectively. In the former solvent, it is often seen as a 1:1:1 triplet, with 2JH,D ) 1 Hz.
b 2,6-Dimethyl-4-tert-butylphenol. c The signals from exchangeable protons were not always identified. d In some cases (see note a), the
coupling interaction between the CH2 and the OH protons may be observed (J ) 5 Hz). e In CD3CN, the OH proton was seen as a multiplet
at 2.69, and extra coupling was also apparent on the methylene peak. f Long-chain, linear aliphatic hydrocarbons. Their solubility in
DMSO was too low to give visible peaks. g Hexamethylphosphoramide. h In some cases (see notes a, d), the coupling interaction between
the CH3 and the OH protons may be observed (J ) 5.5 Hz). i Poly(dimethylsiloxane). Its solubility in DMSO was too low to give visible
peaks.

show their degree of variability. Occasionally, in order


to distinguish between peaks whose assignment was

ambiguous, a further 1-2 L of a specific substrate were


added and the spectra run again.

7514 J. Org. Chem., Vol. 62, No. 21, 1997

Notes
Table 2.

solvent signals
acetic acid

CO
CH3
acetone
CO
CH3
acetonitrile
CN
CH3
benzene
CH
tert-butyl alcohol
C
CH3
tert-butyl methyl ether OCH3
C
CCH3
BHT
C(1)
C(2)
CH(3)
C(4)
CH3Ar
CH3C
C
chloroform
CH
cyclohexane
CH2
1,2-dichloroethane
CH2
dichloromethane
CH2
diethyl ether
CH3
CH2
diglyme
CH3
CH2
CH2
1,2-dimethoxyethane
CH3
CH2
dimethylacetamide
CH3
CO
NCH3
NCH3
dimethylformamide
CH
CH3
CH3
dimethyl sulfoxide
CH3
dioxane
CH2
ethanol
CH3
CH2
ethyl acetate
CH3CO
CO
CH2
CH3
ethyl methyl ketone
CH3CO
CO
CH2CH3
CH2CH3
ethylene glycol
CH2
grease
CH2
n-hexane
CH3
CH2(2)
CH2(3)
HMPAb
CH3
methanol
CH3
nitromethane
CH3
n-pentane
CH3
CH2(2)
CH2(3)
2-propanol
CH3
CH
pyridine
CH(2)
CH(3)
CH(4)
silicone grease
CH3
tetrahydrofuran
CH2
CH2O
toluene
CH3
C(i)
CH(o)
CH(m)
CH(p)
triethylamine
CH3
CH2
a

See footnotes for Table 1.

CDCl3

(CD3)2CO

77.16 ( 0.06

29.84 ( 0.01
206.26 ( 0.13
172.31
20.51
205.87
30.60
117.60
1.12
129.15
68.13
30.72
49.35
72.81
27.24
152.51
138.19
129.05
126.03
21.31
31.61
35.00
79.19
27.51
45.25
54.95
15.78
66.12
58.77
71.03
72.63
58.45
72.47
21.51
170.61
34.89
37.92
162.79
36.15
31.03
41.23
67.60
18.89
57.72
20.83
170.96
60.56
14.50
29.30
208.30
36.75
8.03
64.26
30.73
14.34
23.28
32.30
37.04
49.77
63.21
14.29
22.98
34.83
25.67
63.85
150.67
124.57
136.56
1.40
26.15
68.07
21.46
138.48
129.76
129.03
126.12
12.49
47.07

175.99
20.81
207.07
30.92
116.43
1.89
128.37
69.15
31.25
49.45
72.87
26.99
151.55
135.87
125.55
128.27
21.20
30.33
34.25
77.36
26.94
43.50
53.52
15.20
65.91
59.01
70.51
71.90
59.08
71.84
21.53
171.07
35.28
38.13
162.62
36.50
31.45
40.76
67.14
18.41
58.28
21.04
171.36
60.49
14.19
29.49
209.56
36.89
7.86
63.79
29.76
14.14
22.70
31.64
36.87
50.41
62.50
14.08
22.38
34.16
25.14
64.50
149.90
123.75
135.96
1.04
25.62
67.97
21.46
137.89
129.07
128.26
125.33
11.61
46.25

b 2J
PC

13C

NMR Dataa
(CD3)2SO

C6D6

39.52 ( 0.06 128.06 ( 0.02


171.93
20.95
206.31
30.56
117.91
1.03
128.30
66.88
30.38
48.70
72.04
26.79
151.47
139.12
127.97
124.85
20.97
31.25
34.33
79.16
26.33
45.02
54.84
15.12
62.05
57.98
69.54
71.25
58.01
17.07
21.29
169.54
37.38
34.42
162.29
35.73
30.73
40.45
66.36
18.51
56.07
20.68
170.31
59.74
14.40
29.26
208.72
35.83
7.61
62.76
29.20
13.88
22.05
30.95
36.42
48.59
63.28
13.28
21.70
33.48
25.43
64.92
149.58
123.84
136.05
25.14
67.03
20.99
137.35
128.88
128.18
125.29
11.74
45.74

) 3 Hz. c Reference material; see text.

175.82
20.37
204.43
30.14
116.02
0.20
128.62
68.19
30.47
49.19
72.40
27.09
152.05
136.08
128.52
125.83
21.40
31.34
34.35
77.79
27.23
43.59
53.46
15.46
65.94
58.66
70.87
72.35
58.68
72.21
21.16
169.95
34.67
37.03
162.13
35.25
30.72
40.03
67.16
18.72
57.86
20.56
170.44
60.21
14.19
28.56
206.55
36.36
7.91
64.34
30.21
14.32
23.04
31.96
36.88
49.97
61.16
14.25
22.72
34.45
25.18
64.23
150.27
123.58
135.28
1.38
25.72
67.80
21.10
137.91
129.33
128.56
125.68
12.35
46.77

CD3CN

CD3OD

1.32 ( 0.02
118.26 ( 0.02
173.21
20.73
207.43
30.91
118.26
1.79
129.32
68.74
30.68
49.52
73.17
27.28
152.42
138.13
129.61
126.38
21.23
31.50
35.05
79.17
27.63
45.54
55.32
15.63
66.32
58.90
70.99
72.63
58.89
72.47
21.76
171.31
35.17
38.26
163.31
36.57
31.32
41.31
67.72
18.80
57.96
21.16
171.68
60.98
14.54
29.60
209.88
37.09
8.14
64.22
30.86
14.43
23.40
32.36
37.10
49.90
63.66
14.37
23.08
34.89
25.55
64.30
150.76
127.76
136.89

49.00(0.01

26.27
68.33
21.50
138.90
129.94
129.23
126.28
12.38
47.10

175.11
20.56
209.67
30.67
118.06
0.85
129.34
69.40
30.91
49.66
74.32
27.22
152.85
139.09
129.49
126.11
21.38
31.15
35.36
79.44
27.96
45.11
54.78
15.46
66.88
59.06
71.33
72.92
59.06
72.72
21.32
173.32
35.50
38.43
164.73
36.89
31.61
40.45
68.11
18.40
58.26
20.88
172.89
61.50
14.49
29.39
212.16
37.34
8.09
64.30
31.29
14.45
23.68
32.73
37.00
49.86
63.08
14.39
23.38
35.30
25.27
64.71
150.07
125.53
138.35
2.10
26.48
68.83
21.50
138.85
129.91
129.20
126.29
11.09
46.96

D2O

177.21
21.03
215.94
30.89
119.68
1.47
70.36
30.29
49.37
75.62
26.60

14.77
66.42
58.67
70.05
71.63
58.67
71.49
21.09
174.57
35.03
38.76
165.53
37.54
32.03
39.39
67.19
17.47
58.05
21.15
175.26
62.32
13.92
29.49
218.43
37.27
7.87
63.17

36.46
49.50c
63.22

24.38
64.88
149.18
125.12
138.27
25.67
68.68

9.07
47.19

Notes

For D2O solutions there is no accepted reference for


carbon chemical shifts. We suggest the addition of a drop
of methanol, and the position of its signal to be defined
as 49.50 ppm; on this basis, the entries in Table 2 were
recorded. The chemical shifts thus obtained are, on the
whole, very similar to those for the other solvents.
Alternatively, we suggest the use of dioxane when the
methanol peak is expected to fall in a crowded area of
the spectrum. We also report the chemical shifts of
sodium formate (171.67 ppm), sodium acetate (182.02 and
23.97 ppm), sodium carbonate (168.88 ppm), sodium
bicarbonate (161.08 ppm), and sodium 3-(trimethylsilyl)propanesulfonate [54.90, 19.66, 15.56 (methylenes 1, 2,
and 3, respectively), and -2.04 ppm (methyls)], in D2O.
Temperature Dependence of HDO Chemical
Shifts. We recorded the 1H spectrum of a sample of D2O,
containing a crystal of sodium 3-(trimethylsilyl)propanesulfonate as reference, as a function of temperature. The

J. Org. Chem., Vol. 62, No. 21, 1997 7515

data are shown in Figure 1. The solid line connecting


the experimental points corresponds to the equation

) 5.060 - 0.0122T + (2.11 10-5)T2

(1)

which reproduces the measured values to better than 1


ppb. For the 0 - 50oC range, the simpler

) 5.051 - 0.0111T

(2)

gives values correct to 10 ppb. For both equations, T is


the temperature in C.

Acknowledgment. Generous support for this work


by the Minerva Foundation and the Otto Mayerhoff
Center for the Study of Drug-Receptor Interactions at
Bar-Ilan University is gratefully acknowledged.
JO971176V

Supporting Information

NMR Chemical Shifts of Trace Impurities: Common Laboratory Solvents,


Organics, and Gases in Deuterated Solvents Relevant to the
Organometallic Chemist

Gregory R. Fulmer,*,1 Alexander J. M. Miller,2 Nathaniel H. Sherden,2 Hugo E.


Gottlieb,3 Abraham Nudelman,3 Brian M. Stoltz,2 John E. Bercaw,2 and Karen I.
Goldberg1

Department of Chemistry, University of Washington, Box 351700, Seattle, Washington 98195-1700;

Arnold and Mabel Beckman Laboratories of Chemical Synthesis, and Caltech Center for Catalysis and

Chemical Synthesis, Division of Chemistry and Chemical Engineering California Institute of Technology,
Pasadena, California 91125;
3

Department of Chemistry, Bar Ilan University, Ramat Gan 52900, Israel.

Corrections and Comments ........................................................................................................ S2


1

H NMR Data (Table S1) ............................................................................................................ S3

13

C NMR Data (Table S2) ........................................................................................................... S5

Individual Solvent Tables NMR Data Sorted by Chemical Shift (Tables S3S26) ............ S7
References .................................................................................................................................. S19

S1

Corrections and Comments


In the preparation of this manuscript, several errors were discovered in the
original paper1 and are reported herein. While comparing the 1H NMR spectral data
obtained in toluene-d8 to that in C6D6, it was discovered that the 1H NMR chemical shifts
for acetic acid (CH3), acetonitrile (CH3) and tert-butyl alcohol (OH) in C6D6 had each
been misreported at 1.55 ppm in the original paper; the values have now been correctly
listed as 1.52, 0.58, and 0.63 ppm, respectively. The original paper's assignments for
BHT's C(3,5) and C(4) in C6D6, (CD3)2CO, (CD3)2SO, CD3CN, and CD3OD were
reversed and are now corrected. The resonances for 1,2-dimethoxyethane (CH2) in
(CD3)2CO, silicone grease (CH3) in CDCl3, and 2-propanol (CH3) in CD3OD have been
corrected and are reported as 72.47, 1.04, and 1.15 ppm, respectively. No other
significant differences were discovered when comparing our data to that which had been
previously reported; however, we have additionally provided the OH resonance for
ethanol in C6D6 (0.50 ppm), the CH3 resonance for silicone grease in (CD3)2SO (0.06
ppm), and replaced the grease entry (formerly motor oil1) with VWR vacuum pump oil
#19, which is now reported in each deuterated solvent.

S2

Table S1. 1H NMR Data2


proton

mult

THF-d 8
1.72
3.58

CD2Cl2
5.32

CDCl3
7.26

s
s
s
s
ddt
ddt
ddt
ddd
s
s
m
m
m
s
s
s5
s
s5
s
s
s
s5
s
s
s
s
s
t
m
m
ddt
ddt
ddt
ddd
s
s
t, 7
q, 7
m
m
s
s
s
s
s
s
s
s
s
s
s
s
s
s
s
t, 7
q, 76
s5,6
s
q, 7
t, 7
s
q, 7
t, 7
s
s7
dd
dd
m
br s
s
s

2.46
1.89
2.05
1.95
5.90
5.27
5.15
4.50
1.98
9.98
7.867.88
7.517.55
7.607.64
7.31
1.15
3.16
6.68
5.64
3.68
1.40
6.92
5.81
2.21
1.40
7.89
3.57
1.44
2.24
1.771.82
1.681.71
5.92
5.31
5.19
4.58
3.77
5.51
1.12
3.38
3.43
3.53
3.28
3.28
3.43
1.94
2.95
2.82
3.69
3.65
3.35
7.91
2.88
2.76
2.45
3.56
0.85
1.10
3.51
3.30
1.94
4.04
1.19
2.03
2.39
0.96
5.36
3.48
7.48
6.37
0.850.91
1.29
2.18
0.07

1.52
2.06
2.12
1.97
5.92
5.31
5.22
4.55
2.05
10.01
7.877.89
7.537.57
7.637.67
7.35
1.24
6.73
4.76
3.73
1.42
6.97
5.00
2.25
1.42
7.32
3.59
1.44
2.29
1.811.87
1.691.72
5.95
5.35
5.26
4.61
3.76
5.33
1.15
3.43
3.57
3.50
3.33
3.34
3.49
2.02
2.97
2.87
3.75
3.72
3.37
7.96
2.91
2.82
2.55
3.65
0.85
1.19
3.66
1.33
2.00
4.08
1.23
2.09
2.43
1.00
5.40
3.66
7.46
6.41
0.840.90
1.27
2.20
0.07

1.56
2.10
2.17
2.10
5.93
5.32
5.24
4.57
2.09
10.03
7.887.91
7.517.57
7.617.65
7.36
1.28
6.76
4.76
3.77
1.44
6.98
5.01
2.27
1.43
7.26
3.67
1.43
2.33
1.841.86
1.711.73
5.94
5.37
5.27
4.64
3.73
5.30
1.21
3.48
3.65
3.57
3.39
3.40
3.55
2.09
3.02
2.94
3.79
3.75
3.40
8.02
2.96
2.88
2.62
3.71
0.87
1.25
3.72
1.32
2.05
4.12
1.26
2.14
2.46
1.06
5.40
3.76
7.45
6.40
0.840.87
1.25
2.24
0.07

solvent residual signals

water
acetic acid
acetone
acetonitrile
allyl acetate

OH
CH3
CH3
CH3
CH CH2
CHCH 2(1)
CHCH 2(2)
CH2
CH3
benzaldehyde
HCO
CH(2,6)
CH(3,5)
CH(4)
benzene
CH
CH3
tert -butyl alcohol
OH
BHA
ArH
OH
ArOCH3
ArC(CH3)3
BHT
ArH
OH
ArCH3
ArC(CH3)3
chloroform
CH
CH2
18-crown-6
CH2
cyclohexane
CH2(2,6)
cyclohexanone
CH2(3,5)
CH2(4)
CH CH2
diallyl carbonate
CHCH 2(1)
CHCH 2(2)
CH2
CH2
1,2-dichloroethane
CH2
dichloromethane
CH3
diethyl ether
CH2
CH2
diglyme
CH2
OCH3
CH3
1,2-dimethoxyethane
CH2
CH3CO
dimethylacetamide
NCH3
NCH3
CH3
dimethyl carbonate
CH3
dimethyl malonate
CH2
dimethylformamide
CH
CH3
CH3
CH3
dimethyl sulfoxide
CH2
1,4-dioxane
CH3
ethane
CH3
ethanol
CH2
OH
CH3CO
ethyl acetate
CH 2CH3
CH2CH 3
CH3CO
ethyl methyl ketone
CH 2CH3
CH2CH 3
CH2
ethylene
CH2
ethylene glycol
furan
CH(2,5)
CH(3,4)
CH3
H grease8
CH2
CH3
hexamethylbenzene
CH3
hexamethyldisiloxane

S3

toluene-d 8
2.08
6.97
7.01
7.09
0.43
1.57
1.57
0.69
5.674
5.05
4.94
4.34
1.63
9.57
7.457.47
6.956.99
7.037.07
7.12
1.03
0.58
6.83
4.45
3.48
1.34
6.99
4.72
2.23
1.36
6.10
3.36
1.40
1.95
1.331.39
1.161.20
5.63
5.09
4.92
4.34
2.91
4.32
1.10
3.25
3.43
3.31
3.12
3.12
3.31
1.59
2.56
2.11
3.31
3.24
2.92
7.57
2.37
1.96
1.64
3.33
0.81
0.97
3.36
0.83
1.69
3.87
0.94
1.59
1.82
0.84
5.25
3.36
7.10
6.07
0.890.96
1.33
2.10
0.10

C6D6
7.16

C6D5Cl
6.96
6.99
7.14

0.40
1.52
1.55
0.58
5.684
5.06
4.94
4.38
1.63
9.64
7.497.53
6.936.99
7.017.07
7.15
1.05
0.63
6.93
4.53
3.48
1.41
7.05
4.79
2.24
1.38
6.15
3.39
1.40
1.98
1.281.37
1.081.16
5.65
5.09
4.92
4.38
2.90
4.27
1.11
3.26
3.46
3.34
3.11
3.12
3.33
1.60
2.57
2.05
3.30
3.23
2.97
7.63
2.36
1.86
1.68
3.35
0.80
0.96
3.34
0.50
1.65
3.89
0.92
1.58
1.81
0.85
5.25
3.41
7.13
6.08
0.900.98
1.32
2.13
0.12

1.03
1.76
1.77
1.21
5.77
5.15
5.04
4.44
1.80
9.77
7.597.61
7.157.19
7.247.28
7.20
1.12
1.30
6.83
4.62
3.61
1.37
6.97
5.50
2.20
1.37
6.74
3.41
1.37
2.08
1.481.53
1.331.37
5.75
5.17
5.03
4.46
3.26
4.77
1.10
3.31
3.49
3.37
3.16
3.17
3.37
1.74
2.65
2.42
3.48
3.41
3.15
7.73
2.51
2.30
2.03
3.45
0.79
1.06
3.51
1.39
1.78
3.96
1.04
1.78
2.06
0.89
5.29
3.58
7.24
6.19
0.860.92
1.30
2.10
0.10

(CD3)2CO (CD3)2SO
2.05
2.50

2.843
1.96
2.09
2.05
5.92
5.29
5.18
4.53
2.02
10.05
7.927.94
7.597.63
7.697.73
7.36
1.18
6.72
5.65
3.72
1.41
6.96
2.22
1.41
8.02
3.59
1.43
2.27
1.791.83
1.701.74
5.96
5.35
5.23
4.62
3.87
5.63
1.11
3.41
3.56
3.47
3.28
3.28
3.46
1.97
3.00
2.83
3.72
3.68
3.42
7.96
2.94
2.78
2.52
3.59
0.83
1.12
3.57
3.39
1.97
4.05
1.20
2.07
2.45
0.96
5.38
3.28
7.56
6.43
0.90
1.29
2.17
0.07

3.333
1.91
2.09
2.07
5.91
5.29
5.20
4.52
2.03
10.02
7.917.93
7.617.67
7.697.75
7.37
1.11
4.19
6.62
6.52
3.66
1.36
6.87
6.65
2.18
1.36
8.32
3.51
1.40
2.25
1.741.78
1.641.66
5.93
5.33
5.25
4.61
3.90
5.76
1.09
3.38
3.51
3.38
3.24
3.24
3.43
1.96
2.94
2.78
3.69
3.65
3.53
7.95
2.89
2.73
2.54
3.57
0.82
1.06
3.44
4.63
1.99
4.03
1.17
2.07
2.43
0.91
5.41
3.34
7.67
6.47
0.820.88
1.24
2.14
0.06

CD3CN
1.94

TFE-d 3
5.02
3.88

CD3OD
3.31

D2O
4.79

2.13
1.96
2.08
1.96
5.93
5.29
5.21
4.53
2.02
10.01
7.897.91
7.577.61
7.677.71
7.37
1.16
2.18
6.73
4.98
3.72
1.40
6.97
5.20
2.22
1.39
7.58
3.51
1.44
2.27
1.791.84
1.671.72
5.96
5.34
5.25
4.61
3.81
5.44
1.12
3.42
3.53
3.45
3.29
3.28
3.45
1.97
2.96
2.83
3.72
3.68
3.38
7.92
2.89
2.77
2.50
3.60
0.85
1.12
3.54
2.47
1.97
4.06
1.20
2.06
2.43
0.96
5.41
3.51
7.52
6.44
2.19
0.07

3.66
2.06
2.19
1.95
5.93
5.32
5.25
4.58
2.07
9.88
7.907.92
7.567.59
7.687.72
7.36
1.28
2.20
6.87
3.79
1.44
7.06
2.24
1.43
7.33
3.64
1.47
2.38
1.871.92
1.751.78
5.92
5.35
5.28
4.62
3.71
5.24
1.20
3.58
3.67
3.62
3.41
3.40
3.61
2.09
3.05
2.94
3.77
3.76
3.41
7.86
2.98
2.88
2.63
3.76
0.85
1.22
3.71
2.03
4.14
1.26
2.16
2.49
1.05
5.40
3.72
7.44
6.42
0.880.94
1.33
2.24
0.08

4.87
1.99
2.15
2.03
5.94
5.30
5.21
4.56
2.05
10.00
7.907.93
7.567.60
7.667.70
7.33
1.40
6.71
4.85
3.72
1.41
6.92
2.21
1.40
7.90
3.64
1.45
2.34
1.851.87
1.741.76
5.94
5.34
5.25
4.61
3.78
5.49
1.18
3.49
3.61
3.58
3.35
3.35
3.52
2.07
3.31
2.92
3.74
3.72
3.44
7.97
2.99
2.86
2.65
3.66
0.85
1.19
3.60
2.01
4.09
1.24
2.12
2.50
1.01
5.39
3.59
7.49
6.40
0.860.93
1.29
2.19
0.07

2.08
2.22
2.06
5.99
5.37
5.30
4.62
2.13
9.96
7.977.99
7.577.66
7.767.80
1.24
3.80
2.40
1.851.90
1.701.75
5.99
5.40
5.32
4.69
1.17
3.56
3.67
3.61
3.37
3.37
3.60
2.08
3.06
2.90
3.69
3.78
3.60
7.92
3.01
2.85
2.71
3.75
0.82
1.17
3.65
2.07
4.14
1.24
2.19
3.18
1.26
5.44
3.65
7.57
6.51
0.28

n -hexane
HMPA
hydrogen
imidazole
methane
methanol
nitromethane
n -pentane
propane
2-propanol
propylene

pump oil
pyridine

pyrrole

pyrrolidine10
silicone grease
tetrahydrofuran
toluene

triethylamine

0.88
0.89
0.85
CH3
t, 7
0.89
0.89
0.88
0.88
1.26
1.24
1.19
CH2
m
1.29
1.27
1.22
1.28
2.65
2.40
2.47
CH3
d, 9.5
2.58
2.60
2.42
2.59
4.62
4.47
4.49
H2
s
4.55
4.59
4.50
4.54
7.67
7.33
7.53
CH(2)
s
7.48
7.63
7.30
7.62
7.10
6.90
7.01
CH(4,5)
s
6.94
7.07
6.86
7.04
0.22
0.16
0.15
CH4
s
0.19
0.21
0.17
0.17
9
3.49
3.07
3.25
CH3
3.27
3.42
3.03
3.31
s
1.09
1.30
OH
3.02
1.09
3.12
s5,9
4.33
2.94
3.59
CH3
s
4.31
4.31
3.01
4.43
0.88
0.87
0.84
CH3
t, 7
0.89
0.89
0.87
0.88
1.27
1.23
1.23
CH2
m
1.31
1.30
1.25
1.27
0.90
0.86
0.84
CH3
t, 7.3
0.90
0.90
0.89
0.88
1.32
1.26
1.26
CH2
sept, 7.3
1.33
1.32
1.32
1.31
1.22
0.95
1.04
CH3
d, 6
1.08
1.17
0.95
1.10
4.04
3.67
3.82
CH
sept, 6
3.82
3.97
3.65
3.90
1.73
1.55
1.68
CH3
dt, 6.4, 1.5
1.69
1.71
1.55
1.58
4.94
4.95
4.90
CH2(1)
dm, 10
4.89
4.93
4.92
4.91
5.03
5.01
5.00
CH2(2)
dm, 17
4.99
5.03
4.98
4.98
5.83
5.72
5.81
CH
m
5.79
5.84
5.70
5.72
CH3
m
0.860.90 0.840.89 0.830.89 0.880.96 0.910.97 0.880.91
0.87
1.31
CH2
br s
1.29
1.27
1.26
1.30
1.37
1.29
8.51
CH(2,6)
m
8.54
8.59
8.62
8.47
8.53
8.58
6.90
CH(3,5)
m
7.25
7.28
7.29
6.67
6.66
7.35
7.25
CH(4)
m
7.65
7.68
7.68
6.99
6.98
7.76
8.61
NH
br t
9.96
8.69
8.40
7.71
7.80
10.02
6.62
CH(2,5)
m
6.66
6.79
6.83
6.43
6.48
6.77
6.27
CH(3,4)
m
6.02
6.19
6.26
6.27
6.37
6.07
CH2(2,5)
m
2.75
2.82
2.87
2.54
2.54
2.64
1.43
CH2(3,4)
m
1.59
1.67
1.68
1.36
1.33
0.14
CH3
s
0.11
0.09
0.07
0.26
0.29
0.13
3.59
CH2(2,5)
m
3.62
3.69
3.76
3.54
3.57
3.63
1.55
CH2(3,4)
m
1.79
1.82
1.85
1.43
1.40
1.79
2.16
CH3
s
2.31
2.34
2.36
2.11
2.11
2.32
7.017.08 7.107.20
CH(2,4,6)
m
7.10
7.15
7.17
6.967.01
7.02
7.107.17 7.107.20
CH(3,5)
m
7.19
7.24
7.25
7.09
7.13
0.93
CH3
t, 7
0.97
0.99
1.03
0.95
0.96
0.96
2.39
CH2
q, 7
2.46
2.48
2.53
2.39
2.40
2.45

S4

0.86
1.25
2.53
4.61
7.63
7.01
0.20
3.16
4.01
4.42
0.86
1.27
0.87
1.29
1.04
3.78
1.68
4.94
5.03
5.80
0.74
1.15
8.58
7.39
7.79
10.75
6.73
6.01
2.67
1.55
0.06
3.60
1.76
2.30
7.18
7.25
0.93
2.43

0.91
0.90
0.89
1.31
1.29
1.28
2.63
2.64
2.57
4.53
4.56
4.57
7.61
7.67
7.57
7.03
7.05
7.01
0.18
0.20
0.20
3.44
3.34
3.28
2.16
4.28
4.34
4.31
0.90
0.90
0.89
1.33
1.29
1.29
0.90
0.91
0.90
1.33
1.34
1.33
1.20
1.15
1.09
4.05
3.92
3.87
1.70
1.70
1.70
4.93
4.91
4.93
5.03
5.01
5.04
5.87
5.82
5.85
0.85
0.99
0.860.91
1.27
1.41
1.29
8.45
8.57
8.53
7.40
7.33
7.44
7.82
7.73
7.85
9.27
6.84
6.75
6.72
6.24
6.10
6.08
2.75
2.80
3.11
1.93
1.61
1.72
0.16
0.08
0.10
3.78
3.64
3.71
1.91
1.80
1.87
2.33
2.33
2.32
7.107.30 7.107.30
7.16
7.107.30 7.107.30
7.16
1.31
0.96
1.05
3.12
2.45
2.58

2.61
7.78
7.14
0.18
3.34
4.40
0.88
1.30
1.17
4.02
1.70
4.95
5.06
5.90
8.52
7.45
7.87
6.93
6.26
3.07
1.87
3.74
1.88
0.99
2.57

Table S2. 13C{1H} NMR Data2


carbon
solvent signals

acetic acid
acetone
acetonitrile
allyl acetate

benzaldehyde

benzene
tert -butyl alcohol
BHA

BHT

carbon dioxide
carbon disulfide
carbon tetrachloride
chloroform
18-crown-6
cyclohexane
cyclohexanone

diallyl carbonate

1,2-dichloroethane
dichloromethane
diethyl ether
diglyme

1,2-dimethoxyethane
dimethylacetamide

dimethyl carbonate
dimethyl malonate

dimethylformamide

dimethyl sulfoxide
1,4-dioxane
ethane
ethanol

CO
CH3
CO
CH3
CN
CH3
CO
C HCH2
CHC H2
CH2
CH3
HCO
C(1)
CH(2,6)
CH(3,5)
CH (4)
CH
(CH3)3C
(C H3)3C
C(1)
C(2,6)
CH(3,5)
C(4)
CH3O
(C H3)3C
(CH3)3C
C(1)
C(2,6)
CH(3,5)
C(4)
CH3Ar
(C H3)3C
(CH3)3C
CO2
CS2
CCl4
CH
CH2
CH2
CO
CH2(2,6)
CH2(3,5)
CH2(4)
CO
C HCH2
CHC H2
CH2
CH2
CH2
CH3
CH2
CH3
CH2
CH2
CH3
CH2
CH3
CO
NCH3
NCH3
CO
CH3
CO2
CH3
CH2
CH
CH3
CH3
CH3
CH2
CH3
CH3
CH2

S5

THF-d 8
67.21
25.31

CD2Cl2
53.84

CDCl3
77.16

171.69
20.13
204.19
30.17
116.79
0.45
170.14
133.90
117.58
65.31
20.45
191.95
137.78
129.98
129.56
134.67
128.84
67.50
30.57
154.07
148.62
110.94
140.07
55.39
30.65
35.51
152.48
137.93
125.71
128.64
21.21
31.55
34.91
125.69
193.37
96.89
79.24
71.34
27.58
208.79
42.17
27.69
25.76
155.36
133.08
117.70
68.58
44.64
54.67
15.49
66.14
58.72
71.17
72.72
58.72
72.58
21.15
169.77
34.60
37.56
156.91
54.58
167.14
52.07
41.15
161.96
35.65
30.70
41.21
67.65
6.79
18.90
57.60

175.85
20.91
206.78
31.00
116.92
2.03
170.83
132.94
118.00
65.36
21.06
192.61
136.98
129.98
129.42
134.79
128.68
69.11
31.46
153.05
148.06
110.93
137.77
55.88
30.37
34.91
151.92
136.32
125.84
128.73
21.27
30.54
34.56
125.26
192.95
96.52
77.99
70.47
27.38
211.82
42.31
27.47
25.42
155.15
132.24
118.75
68.76
44.35
54.24
15.44
66.11
58.95
70.70
72.25
59.02
72.24
21.64
171.05
35.23
38.22
156.73
55.09
167.32
52.75
41.48
162.57
36.56
31.39
41.33
67.47
6.91
18.69
58.57

175.99
20.81
207.07
30.92
116.43
1.89
170.81
132.33
118.34
65.28
21.02
192.67
136.58
129.91
129.16
134.64
128.37
69.15
31.25
152.57
147.85
110.69
137.36
55.70
30.32
34.72
151.55
135.87
125.55
128.27
21.20
30.33
34.25
124.99
192.83
96.34
77.36
70.55
26.94
212.57
41.97
27.00
24.97
154.88
131.58
118.96
68.55
43.50
53.52
15.20
65.91
59.01
70.51
71.90
59.08
71.84
21.53
171.07
35.28
38.13
156.45
54.89
167.18
52.57
41.11
162.62
36.50
31.45
40.76
67.14
6.89
18.41
58.28

toluene-d 8
137.48
128.87
127.96
125.13
20.43
175.30
20.27
204.00
30.03
115.76
0.03
169.44
132.98
117.49
64.87
20.21
191.09
137.12
129.61
128.68
133.88
128.57
68.12
30.49
153.50
148.06
110.99
137.34
55.04
30.30
34.69
152.06
136.12
125.79
128.44
21.42
31.39
34.39
124.86
192.71
96.57
77.89
70.86
27.31
208.60
41.78
27.05
25.15
155.15
132.30
118.04
68.20
43.40
53.47
15.47
65.94
58.62
70.92
72.39
58.63
72.25
21.05
169.65
34.58
36.98
156.61
54.13
166.49
51.76
40.88
161.93
35.22
30.64
40.41
67.17
6.94
18.78
57.81

C6D6
128.06

C6D5Cl
134.19
129.26
128.25
125.96

(CD3)2CO
29.84
206.26

(CD3)2SO
39.52

CD3CN
1.32
118.26

TFE-d 3
61.50
126.28

CD3OD
49.00

D2O
-

175.82
20.37
204.43
30.14
116.02
0.20
169.67
132.90
117.64
64.92
20.37
191.43
137.05
129.65
128.95
133.95
128.62
68.19
30.47
153.62
148.13
111.15
137.50
55.27
30.35
34.72
152.05
136.08
125.83
128.52
21.40
31.34
34.35
124.76
192.69
96.44
77.79
70.59
27.23
209.10
41.83
27.00
25.03
155.24
132.18
118.22
68.28
43.59
53.46
15.46
65.94
58.66
70.87
72.35
58.68
72.21
21.16
169.95
34.67
37.03
156.71
54.30
166.66
51.86
41.04
162.13
35.25
30.72
40.03
67.16
6.96
18.72
57.86

175.67
20.40
204.83
30.12
115.93
0.63
169.59
132.69
117.63
64.86
20.40
191.24
136.78
129.49
128.87
134.02
128.38
68.19
31.13
153.19
147.87
110.84
137.29
55.08
30.21
34.56
151.69
135.92
125.58
128.26
21.10
30.19
34.11
126.08
192.49
96.38
77.67
70.55
26.99
209.30
41.79
27.02
25.07
154.87
131.93
118.22
68.19
43.60
53.54
15.35
65.79
58.42
70.56
72.07
58.31
71.81
21.03
169.79
34.59
37.13
156.36
54.23
166.51
51.89
40.93
162.01
35.45
30.71
40.27
66.95
6.91
18.55
57.63

172.31
20.51
205.87
30.60
117.60
1.12
170.61
133.76
117.81
65.28
20.68
192.95
137.66
130.23
129.90
135.14
129.15
68.13
30.72
153.97
148.48
111.00
140.32
55.51
30.64
35.45
152.51
138.19
126.03
129.05
21.31
31.61
35.00
125.81
193.58
96.65
79.19
71.25
27.51
210.36
42.24
27.68
25.59
155.48
133.16
118.53
68.78
45.25
54.95
15.78
66.12
58.77
71.03
72.63
58.45
72.47
21.51
170.61
34.89
37.92
157.04
54.95
167.58
52.47
41.43
162.79
36.15
31.03
41.23
67.60
6.88
18.89
57.72

171.93
20.95
206.31
30.56
117.91
1.03
169.97
132.71
117.64
64.32
20.54
193.08
136.20
129.45
129.10
134.52
128.30
66.88
30.38
152.53
147.44
109.80
141.16
54.89
30.30
34.76
151.47
139.12
124.85
127.97
20.97
31.25
34.33
124.21
192.63
95.44
79.16
69.85
26.33
210.63
41.32
26.46
24.32
154.16
132.18
118.32
67.86
45.02
54.84
15.12
62.05
57.98
69.54
71.25
58.03
71.17
21.29
169.54
34.42
37.38
155.76
54.63
166.91
52.08
40.72
162.29
35.73
30.73
40.45
66.36
6.61
18.51
56.07

173.21
20.73
207.43
30.91
118.26
1.79
171.32
133.83
118.06
65.55
21.02
193.64
137.62
130.42
130.07
135.40
129.32
68.74
30.68
154.02
148.39
111.35
140.20
55.94
30.55
35.48
152.42
138.13
126.38
129.61
21.23
31.50
35.05
125.89
193.60
96.68
79.17
71.22
27.63
211.99
42.44
27.80
25.62
155.66
133.20
118.86
69.09
45.54
55.32
15.63
66.32
58.90
70.99
72.63
58.89
72.47
21.76
171.31
35.17
38.26
157.26
55.39
168.07
52.95
41.77
163.31
36.57
31.32
41.31
67.72
6.99
18.80
57.96

177.96
20.91
32.35
214.98
118.95
1.00
175.98
133.33
119.39
67.61
21.10
197.63
137.84
131.78
130.82
137.17
129.84
72.35
31.07
153.74
150.52
112.90
140.23
57.55
30.80
36.07
153.46
138.59
127.11
130.62
21.34
31.01
35.69
126.92
196.26
97.74
78.83
70.80
28.34
221.30
43.16
28.56
26.00
157.39
132.72
120.15
70.69
45.28
54.46
15.33
67.55
59.40
73.05
71.33
59.52
72.87
21.40
175.74
36.28
39.06
159.04
56.17
170.88
54.00
42.13
166.01
37.76
30.96
40.06
68.52
7.01
18.11
59.68

175.11
20.56
209.67
30.67
118.06
0.85
172.41
133.71
118.22
66.14
20.71
194.11
137.96
130.64
130.12
135.60
129.34
69.40
30.91
154.34
149.04
111.30
141.36
55.96
30.82
35.83
152.85
139.09
126.11
129.49
21.38
31.15
35.36
126.31
193.82
97.21
79.44
71.47
27.96
214.69
42.61
28.16
25.86
156.28
133.25
118.74
69.35
45.11
54.78
15.46
66.88
59.06
71.33
72.92
59.06
72.72
21.32
173.32
35.50
38.43
157.91
55.25
168.70
52.83
41.60
164.73
36.89
31.61
40.45
68.11
6.98
18.40
58.26

177.21
21.03
215.94
30.89
119.68
1.47
174.78
132.48
119.03
66.52
21.00
191.67
136.11
130.09
129.48
134.70
70.36
30.29
197.25
96.73
70.14
221.22
42.02
27.50
24.77
157.78
132.76
118.75
68.81
14.77
66.42
58.67
70.05
71.63
58.67
71.49
21.09
174.57
35.03
38.76
163.96
55.81
170.12
53.65
42.13
165.53
37.54
32.03
39.39
67.19
17.47
58.05

C H3CO
CO
CH2
CH3
C H3CO
ethyl methyl ketone
CO
C H2CH3
CH2C H3
CH2
ethylene
CH2
ethylene glycol
furan
CH(2,5)
CH(3,4)
CH2
H grease8
hexamethylbenzene
C
CH3
CH3
hexamethyldisiloxane
CH3
n -hexane
CH2(2,5)
CH2(3,4)
HMPA11
CH3
imidazole
CH(2)
CH(4,5)
CH4
methane
CH3
methanol
CH3
nitromethane
CH3
n -pentane
CH2(2,4)
CH2(3)
CH3
propane
CH2
CH3
2-propanol
CH
CH3
propylene
CH2
CH
CH2
pump oil
pyridine
CH(2,6)
CH(3,5)
CH(4)
pyrrole
CH(2,5)
CH(3,4)
pyrrolidine10
CH2(2,5)
CH2(3,4)
CH3
silicone grease
CH2(2,5)
tetrahydrofuran
CH2(3,4)
CH3
toluene
C(1)
CH(2,6)
CH(3,5)
CH(4)
CH3
triethylamine
CH2
ethyl acetate

S6

20.45
170.32
60.30
14.37
28.92
207.05
36.59
7.87
123.09
64.35
143.26
109.88
30.45
131.88
16.71
1.83
14.22
23.33
32.34
36.89
135.72
122.20
4.90
49.64
62.49
14.18
23.00
34.87
16.60
16.82
25.70
66.14
19.27
115.74
134.02
30.63
150.57
124.08
135.99
118.03
107.74
45.82
26.17
1.20
68.03
26.19
21.29
138.24
129.47
128.71
125.84
12.51
47.18

21.15
171.24
60.63
14.37
29.55
209.57
37.01
7.94
123.20
64.08
142.98
109.86
30.14
132.09
16.93
1.96
14.28
23.07
32.01
36.99
135.76
122.16
4.33
50.45
63.03
14.24
22.77
34.57
16.63
16.63
25.43
64.67
19.47
115.70
134.21
30.13
150.27
124.06
136.16
117.93
108.02
47.02
25.83
1.22
68.16
25.98
21.53
138.36
129.35
128.54
125.62
12.12
46.75

21.04
171.36
60.49
14.19
29.49
209.56
36.89
7.86
123.13
63.79
142.71
109.57
29.71
132.21
16.98
1.97
14.14
22.70
31.64
36.87
135.38
122.00
4.63
50.41
62.50
14.08
22.38
34.16
16.63
16.37
25.14
64.50
19.50
115.74
133.91
29.84
149.90
123.75
135.96
117.77
107.98
46.93
25.56
1.19
67.97
25.62
21.46
137.89
129.07
128.26
125.33
11.61
46.25

20.46
170.02
60.08
14.23
28.74
206.31
36.32
7.89
122.92
64.29
142.65
109.63
30.31
131.72
16.84
1.99
14.34
23.12
32.06
36.80
135.57
122.13
4.34
49.90
61.14
14.27
22.79
34.54
16.65
16.63
25.24
64.12
19.32
115.89
133.61
30.33
150.25
123.46
135.17
117.61
108.15
47.12
25.75
1.37
67.75
25.79
21.37
137.84
129.33
128.51
125.66
12.39
46.82

20.56
170.44
60.21
14.19
28.56
206.55
36.36
7.91
122.96
64.34
142.73
109.67
30.22
131.79
16.95
2.05
14.32
23.04
31.96
36.88
135.76
122.16
4.29
49.97
61.16
14.25
22.72
34.45
16.66
16.60
25.18
64.23
19.38
115.92
133.69
30.24
150.27
123.58
135.28
117.78
108.21
46.86
25.65
1.38
67.80
25.72
21.10
137.91
129.33
128.56
125.68
12.35
46.77

20.50
170.20
60.06
14.07
28.82
206.87
36.39
7.79
122.95
64.03
142.49
109.64
30.11
131.54
16.68
1.92
14.18
22.86
31.77
36.64
135.50
121.96
4.33
49.66
61.68
14.10
22.54
34.26
16.56
16.48
25.14
64.18
19.32
115.86
133.57
30.11
149.93
123.49
135.32
117.65
108.03
46.75
25.59
1.09
67.64
25.68
21.23
137.65
129.12
128.31
125.43
11.87
46.36

20.83
170.96
60.56
14.50
29.30
208.30
36.75
8.03
123.47
64.26
143.49
110.24
132.22
16.86
2.01
14.34
23.28
32.30
37.04
135.89
122.31
5.33
49.77
63.21
14.29
22.98
34.83
16.68
16.78
25.67
63.85
19.42
116.03
134.34
30.36
150.67
124.57
136.56
117.98
108.04
1.40
68.07
26.15
21.46
138.48
129.76
129.03
126.12
12.49
47.07

20.68
170.31
59.74
14.40
29.26
208.72
35.83
7.61
123.52
62.76
142.82
109.62
131.10
16.60
1.96
13.88
22.05
30.95
36.42
135.15
121.55
4.01
48.59
63.28
13.28
21.70
33.48
16.34
15.67
25.43
64.92
19.20
116.07
133.55
29.33
149.58
123.84
136.05
117.32
107.07
46.51
25.26
67.03
25.14
20.99
137.35
128.88
128.18
125.29
11.74
45.74

21.16
171.68
60.98
14.54
29.60
209.88
37.09
8.14
123.69
64.22
143.74
110.49
132.61
16.94
2.07
14.43
23.40
32.36
37.10
136.33
122.78
4.61
49.90
63.66
14.37
23.08
34.89
16.73
16.91
25.55
64.30
19.48
116.12
134.78
30.86
150.76
127.76
136.89
118.47
108.31
47.57
26.34
68.33
26.27
21.50
138.90
129.94
129.23
126.28
12.38
47.10

21.18
175.55
62.70
14.36
29.64
218.31
38.23
8.29
124.08
64.87
144.22
111.06
134.04
17.04
2.09
14.63
24.06
33.17
37.21
136.58
122.93
5.88
50.67
63.17
14.54
23.75
35.76
16.93
17.46
25.21
66.69
19.63
116.38
136.00
31.85
149.76
126.27
139.62
119.61
108.85
47.43
25.73
2.87
69.53
26.69
21.62
139.92
130.58
129.79
126.82
9.51
48.45

20.88
172.89
61.50
14.49
29.39
212.16
37.34
8.09
123.46
64.30
143.68
110.33
132.53
16.90
1.99
14.45
23.68
32.73
37.00
136.31
122.60
4.90
49.86
63.08
14.39
23.38
35.30
16.80
17.19
25.27
64.71
19.50
116.04
134.61
31.35
150.07
125.53
138.35
118.28
108.11
47.23
26.29
2.10
68.83
26.48
21.50
138.85
129.91
129.20
126.29
11.09
46.96

21.15
175.26
62.32
13.92
29.49
218.43
37.27
7.87
63.17
143.57
110.23
2.31
36.46
136.65
122.43
49.5012
63.22
24.38
64.88
149.18
125.12
138.27
119.06
107.83
46.83
25.86
68.68
25.67
9.07
47.19

Table S3. THF-d8 (1H NMR data by chemical shift in ppm)


shift
0.07
0.11
0.19
0.85
0.850.91
0.860.90
0.89
0.89
0.90
0.96
0.97
1.08
1.10
1.12
1.15
1.19
1.29
1.29
1.29
1.31
1.33
1.40
1.40
1.44
1.59
1.681.71
1.69
1.72
1.771.82
1.79
1.89
1.94
1.94
1.95
1.98
2.03
2.05
2.18

mult

proton

s
CH3
s
CH3
s
CH4
s
CH3
m
CH3
m
CH3
t, 7
CH3
t, 7
CH3
t, 7.3
CH3
t, 7
CH2CH3
t, 7
CH3
d, 6
CH3
t, 7
CH3
t, 7
CH3
s
CH3
t, 7
CH2CH3
br s
CH2
m
CH2
br s
CH2
m
CH2
sept, 7.3
CH2
s
ArC(CH3)3
s
ArC(CH3)3
s
CH2
m
CH2(3,4)
m
CH2(4)
dt, 6.4, 1.5
CH3
m
CHD(3,4)
m
CH2(3,5)
m
CH2(3,4)
s
CH3
s
CH3CO
s
CH3CO
s
CH3
s
CH3
s
CH3CO
s
CH3
s
CH3

impurity

shift

mult

proton

impurity

shift

mult

proton

impurity

hexamethyldisiloxane
silicone grease
methane
ethane
H grease8
pump oil
n-hexane
n-pentane
propane
ethyl methyl ketone
triethylamine
2-propanol
ethanol
diethyl ether
tert-butyl alcohol
ethyl acetate
H grease8
n-hexane
pump oil
n-pentane
propane
BHA
BHT
cyclohexane
pyrrolidine
cyclohexanone
propylene
THF-d8 residual
cyclohexanone
tetrahydrofuran
acetic acid
dimethylacetamide
ethyl acetate
acetonitrile
allyl acetate
ethyl methyl ketone
acetone
hexamethylbenzene

2.21
2.24
2.31
2.39
2.45
2.46
2.46
2.58
2.75
2.76
2.82
2.88
2.95
3.02
3.16
3.27
3.28
3.28
3.30
3.35
3.38
3.43
3.43
3.48
3.51
3.53
3.56
3.57
3.58
3.62
3.65
3.68
3.69
3.77
3.82
4.04
4.31

s
t
s
q, 7
s
s
q, 7
d, 9.5
m
s
s
s
s
s9
s
s9
s
s
s6
s
q, 7
m
s
s
q, 76
m
s
s
m
m
s
s
s
s
sept, 6
q, 7
s

ArCH3
CH2(2,6)
CH3
CH2CH3
CH3
OH
CH2
CH3
CH2(2,5)
CH3
NCH3
CH3
NCH3
OH
OH
CH3
OCH3
CH3
OH
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CHD(2,5)
CH2(2,5)
CH3
ArOCH3
CH3
CH2
CH
CH2CH3
CH3

BHT
cyclohexanone
toluene
ethyl methyl ketone
dimethyl sulfoxide
water
triethylamine
HMPA
pyrrolidine
dimethylformamide
dimethylacetamide
dimethylformamide
dimethylacetamide
methanol
tert-butyl alcohol
methanol
diglyme
1,2-dimethoxyethane
ethanol
dimethyl malonate
diethyl ether
diglyme
1,2-dimethoxyethane
ethylene glycol
ethanol
diglyme
1,4-dioxane
18-crown-6
THF-d8 residual
tetrahydrofuran
dimethyl malonate
BHA
dimethyl carbonate
1,2-dichloroethane
2-propanol
ethyl acetate
nitromethane

4.50
4.55
4.58
4.89
4.99
5.15
5.19
5.27
5.31
5.36
5.51
5.64
5.79
5.81
5.90
5.92
6.02
6.37
6.66
6.68
6.92
6.94
7.10
7.19
7.25
7.31
7.48
7.48
7.517.55
7.607.64
7.65
7.867.88
7.89
7.91
8.54
9.96
9.98

ddd
s
ddd
dm, 10
dm, 17
ddt
ddt
ddt
ddt
s
s
s
m
s
ddt
ddt
m
dd
m
s
s
s
m
m
m
s
dd
s
m
m
m
m
s
s
m
br t
s

CH2
H2
CH2
CH2(1)
CH2(2)
CHCH2(2)
CHCH2(2)
CHCH2(1)
CHCH2(1)
CH2
CH2
OH
CH
OH
CHCH2
CHCH2
CH(3,4)
CH(3,4)
CH(2,5)
ArH
ArH
CH(4,5)
CH(2,4,6)
CH(3,5)
CH(3,5)
CH
CH(2,5)
CH(2)
CH(3,5)
CH(4)
CH(4)
CH(2,6)
CH
CH
CH(2,6)
NH
HCO

allyl acetate
hydrogen
diallyl carbonate
propylene
propylene
allyl acetate
diallyl carbonate
allyl acetate
diallyl carbonate
ethylene
dichloromethane
BHA
propylene
BHT
allyl acetate
diallyl carbonate
pyrrole
furan
pyrrole
BHA
BHT
imidazole
toluene
toluene
pyridine
benzene
furan
imidazole
benzaldehyde
benzaldehyde
pyridine
benzaldehyde
chloroform
dimethylformamide
pyridine
pyrrole
benzaldehyde

Table S4. THF-d8 (13C{1H} NMR data by chemical shift in ppm)


shift

carbon

impurity

shift

carbon

impurity

shift

carbon

impurity

shift

carbon

impurity

4.90
0.45
1.20
1.83
6.79
7.87
12.51
14.18
14.22
14.37
15.49
16.60
16.71
16.82
18.90
19.27
20.13
20.45
20.45
21.15
21.21
21.29
23.00
23.33
25.31 (p)
25.70
25.76
26.17
26.19
27.58
27.69
28.92

CH4
CH3
CH3
CH3
CH3
CH2CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH2
CH3
CH3
CH3
CH3
CH3CO
CH3
CH3Ar
CH3
CH2(2,4)
CH2(2,5)
CD2(3,4)
CH3
CH2(4)
CH2(3,4)
CH2(3,4)
CH2
CH2(3,5)
CH3CO

methane
acetonitrile
silicone grease
hexamethyldisiloxane
ethane
ethyl methyl ketone
triethylamine
n-pentane
n-hexane
ethyl acetate
diethyl ether
propane
hexamethylbenzene
propane
ethanol
propylene
acetic acid
allyl acetate
ethyl acetate
dimethylacetamide
BHT
toluene
n-pentane
n-hexane
THF-d8 signal
2-propanol
cyclohexanone
pyrrolidine
tetrahydrofuran
cyclohexane
cyclohexanone
ethyl methyl ketone

30.17
30.45
30.57
30.63
30.65
30.70
31.55
32.34
34.60
34.87
34.91
35.51
35.65
36.59
36.89 (d)
37.56
41.15
41.21
42.17
44.64
45.82
47.18
49.64
52.07
54.58
54.67
55.39
57.60
58.72
58.72
60.30
62.49

CH3
CH2
(CH3)3C
CH2
(CH3)3C
CH3
(CH3)3C
CH2(3,4)
NCH3
CH2(3)
(CH3)3C
(CH3)3C
CH3
CH2CH3
CH3
NCH3
CH2
CH3
CH2(2,6)
CH2
CH2(2,5)
CH2
CH3
CH3
CH3
CH2
CH3O
CH2
CH3
CH3
CH2
CH3

acetone
H grease8
tert-butyl alcohol
pump oil
BHA
dimethylformamide
BHT
n-hexane
dimethylacetamide
n-pentane
BHT
BHA
dimethylformamide
ethyl methyl ketone
HMPA11
dimethylacetamide
dimethyl malonate
dimethyl sulfoxide
cyclohexanone
1,2-dichloroethane
pyrrolidine
triethylamine
methanol
dimethyl malonate
dimethyl carbonate
dichloromethane
BHA
ethanol
diglyme
1,2-dimethoxyethane
ethyl acetate
nitromethane

64.35
65.31
66.14
66.14
67.21 (p)
67.50
67.65
68.03
68.58
71.17
71.34
72.58
72.72
79.24
96.89
107.74
109.88
110.94
115.74
116.79
117.58
117.70
118.03
122.20
123.09
124.08
125.69
125.71
125.84
128.64
128.71
128.84

CH2
CH2
CH2
CH
CD2(2,5)
(CH3)3C
CH2
CH2(2,5)
CH2
CH2
CH2
CH2
CH2
CH
CCl4
CH(3,4)
CH(3,4)
CH(3,5)
CH2
CN
CHCH2
CHCH2
CH(2,5)
CH(4,5)
CH2
CH(3,5)
CO2
CH(3,5)
CH(4)
C(4)
CH(3,5)
CH

ethylene glycol
allyl acetate
diethyl ether
2-propanol
THF-d8 signal
tert-butyl alcohol
1,4-dioxane
tetrahydrofuran
diallyl carbonate
diglyme
18-crown-6
1,2-dimethoxyethane
diglyme
chloroform
carbon tetrachloride
pyrrole
furan
BHA
propylene
acetonitrile
allyl acetate
diallyl carbonate
pyrrole
imidazole
ethylene
pyridine
carbon dioxide
BHT
toluene
BHT
toluene
benzene

129.47
129.56
129.98
131.88
133.08
133.90
134.02
134.67
135.72
135.99
137.78
137.93
138.24
140.07
143.26
148.62
150.57
152.48
154.07
155.36
156.91
161.96
167.14
169.77
170.14
170.32
171.69
191.95
193.37
204.19
207.05
208.79

CH(2,6)
CH(3,5)
CH(2,6)
C
CHCH2
CHCH2
CH
CH (4)
CH(2)
CH(4)
C(1)
C(2,6)
C(1)
C(4)
CH(2,5)
C(2,6)
CH(2,6)
C(1)
C(1)
CO
CO
CH
CO2
CO
CO
CO
CO
HCO
CS2
CO
CO
CO

toluene
benzaldehyde
benzaldehyde
hexamethylbenzene
diallyl carbonate
allyl acetate
propylene
benzaldehyde
imidazole
pyridine
benzaldehyde
BHT
toluene
BHA
furan
BHA
pyridine
BHT
BHA
diallyl carbonate
dimethyl carbonate
dimethylformamide
dimethyl malonate
dimethylacetamide
allyl acetate
ethyl acetate
acetic acid
benzaldehyde
carbon disulfide
acetone
ethyl methyl ketone
cyclohexanone

S7

Table S5. CD2Cl2 (1H NMR data by chemical shift in ppm)


shift

mult

0.07
0.09
0.21
0.840.89
0.840.90
0.85
0.89
0.89
0.90
0.99
1.00
1.09
1.15
1.17
1.19
1.23
1.24
1.27
1.27
1.27
1.30
1.32
1.33
1.42
1.42
1.44
1.52
1.691.72
1.67
1.71
1.811.87
1.82
1.97
2.00
2.02
2.05
2.06

proton

s
CH3
s
CH3
s
CH4
m
CH3
m
CH3
s
CH3
t, 7
CH3
t, 7
CH3
t, 7.3
CH3
t, 7
CH3
t, 7
CH2CH3
s9
OH
t, 7
CH3
d, 6
CH3
t, 7
CH3
t, 7
CH2CH3
s
CH3
br s
CH2
m
CH2
br s
CH2
m
CH2
sept, 7.3
CH2
s6
OH
s
ArC(CH3)3
s
ArC(CH3)3
s
CH2
s
OH
m
CH2(4)
m
CH2(3,4)
dt, 6.4, 1.5
CH3
m
CH2(3,5)
m
CH2(3,4)
s
CH3
s
CH3CO
s
CH3CO
s
CH3
s
CH3

impurity

shift

mult

proton

impurity

shift

mult

proton

impurity

hexamethyldisiloxane
silicone grease
methane
pump oil
H grease8
ethane
n-hexane
n-pentane
propane
triethylamine
ethyl methyl ketone
methanol
diethyl ether
2-propanol
ethanol
ethyl acetate
tert-butyl alcohol
H grease8
n-hexane
pump oil
n-pentane
propane
ethanol
BHA
BHT
cyclohexane
water
cyclohexanone
pyrrolidine
propylene
cyclohexanone
tetrahydrofuran
acetonitrile
ethyl acetate
dimethylacetamide
allyl acetate
acetic acid

2.09
2.12
2.20
2.25
2.29
2.34
2.43
2.48
2.55
2.60
2.82
2.82
2.87
2.91
2.97
3.33
3.34
3.37
3.42
3.43
3.49
3.50
3.57
3.59
3.65
3.66
3.66
3.69
3.72
3.73
3.75
3.76
3.97
4.08
4.31
4.55
4.59

s
s
s
s
t
s
q, 7
q, 7
s
d, 9.5
s
m
s
s
s
s
s
s
s9
q, 7
s
m
m
s
s
q, 76
s
m
s
s
s
s
sept, 6
q, 7
s
ddd
s

CH3CO
CH3
CH3
ArCH3
CH2(2,6)
CH3
CH2CH3
CH2
CH3
CH3
CH3
CH2(2,5)
NCH3
CH3
NCH3
OCH3
CH3
CH2
CH3
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2(2,5)
CH3
ArOCH3
CH3
CH2
CH
CH2CH3
CH3
CH2
H2

ethyl methyl ketone


acetone
hexamethylbenzene
BHT
cyclohexanone
toluene
ethyl methyl ketone
triethylamine
dimethyl sulfoxide
HMPA
dimethylformamide
pyrrolidine
dimethylacetamide
dimethylformamide
dimethylacetamide
diglyme
1,2-dimethoxyethane
dimethyl malonate
methanol
diethyl ether
1,2-dimethoxyethane
diglyme
diglyme
18-crown-6
1,4-dioxane
ethanol
ethylene glycol
tetrahydrofuran
dimethyl malonate
BHA
dimethyl carbonate
1,2-dichloroethane
2-propanol
ethyl acetate
nitromethane
allyl acetate
hydrogen

4.61
4.76
4.93
5.00
5.03
5.22
5.26
5.31
5.32
5.33
5.35
5.40
5.84
5.92
5.95
6.19
6.41
6.73
6.79
6.97
7.07
7.15
7.24
7.28
7.32
7.35
7.46
7.537.57
7.63
7.637.67
7.68
7.877.89
7.96
8.59
8.69
10.01

ddd
s
dm, 10
s
dm, 17
ddt
ddt
ddt
t
s
ddt
s
m
ddt
ddt
m
dd
s
m
s
s
m
m
m
s
s
dd
m
s
m
m
m
s
m
br t
s

CH2
OH
CH2(1)
OH
CH2(2)
CHCH2(2)
CHCH2(2)
CHCH2(1)
CDHCl2
CH2
CHCH2(1)
CH2
CH
CHCH2
CHCH2
CH(3,4)
CH(3,4)
ArH
CH(2,5)
ArH
CH(4,5)
CH(2,4,6)
CH(3,5)
CH(3,5)
CH
CH
CH(2,5)
CH(3,5)
CH(2)
CH(4)
CH(4)
CH(2,6)
CH
CH(2,6)
NH
HCO

diallyl carbonate
BHA
propylene
BHT
propylene
allyl acetate
diallyl carbonate
allyl acetate
CD2Cl2 residual
dichloromethane
diallyl carbonate
ethylene
propylene
allyl acetate
diallyl carbonate
pyrrole
furan
BHA
pyrrole
BHT
imidazole
toluene
toluene
pyridine
chloroform
benzene
furan
benzaldehyde
imidazole
benzaldehyde
pyridine
benzaldehyde
dimethylformamide
pyridine
pyrrole
benzaldehyde

Table S6. CD2Cl2 (13C{1H} NMR data by chemical shift in ppm)


shift

carbon

impurity

shift

carbon

impurity

shift

carbon

impurity

shift

carbon

impurity

4.33
1.22
1.96
2.03
6.91
7.94
12.12
14.24
14.28
14.37
15.44
16.63
16.63
16.93
18.69
19.47
20.91
21.06
21.15
21.27
21.53
21.64
22.77
23.07
25.42
25.43
25.83
25.98
27.38
27.47
29.55
30.13

CH4
CH3
CH3
CH3
CH3
CH2CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH2
CH3
CH3
CH3
CH3
CH3
CH3CO
CH3Ar
CH3
CH3
CH2(2,4)
CH2(2,5)
CH2(4)
CH3
CH2(3,4)
CH2(3,4)
CH2
CH2(3,5)
CH3CO
CH2

methane
silicone grease
hexamethyldisiloxane
acetonitrile
ethane
ethyl methyl ketone
triethylamine
n-pentane
n-hexane
ethyl acetate
diethyl ether
propane
propane
hexamethylbenzene
ethanol
propylene
acetic acid
allyl acetate
ethyl acetate
BHT
toluene
dimethylacetamide
n-pentane
n-hexane
cyclohexanone
2-propanol
pyrrolidine
tetrahydrofuran
cyclohexane
cyclohexanone
ethyl methyl ketone
pump oil

30.14
30.37
30.54
31.00
31.39
31.46
32.01
34.56
34.57
34.91
35.23
36.56
36.99 (d)
37.01
38.22
41.33
41.48
42.31
44.35
46.75
47.02
50.45
52.75
53.84 (p)
54.24
55.09
55.88
58.57
58.95
59.02
60.63
63.03

CH2
(CH3)3C
(CH3)3C
CH3
CH3
(CH3)3C
CH2(3,4)
(CH3)3C
CH2(3)
(CH3)3C
NCH3
CH3
CH3
CH2CH3
NCH3
CH3
CH2
CH2(2,6)
CH2
CH2
CH2(2,5)
CH3
CH3
CD2Cl2
CH2
CH3
CH3O
CH2
CH3
CH3
CH2
CH3

H grease8
BHA
BHT
acetone
dimethylformamide
tert-butyl alcohol
n-hexane
BHT
n-pentane
BHA
dimethylacetamide
dimethylformamide
HMPAi
ethyl methyl ketone
dimethylacetamide
dimethyl sulfoxide
dimethyl malonate
cyclohexanone
1,2-dichloroethane
triethylamine
pyrrolidine
methanol
dimethyl malonate
CD2Cl2 signal
dichloromethane
dimethyl carbonate
BHA
ethanol
diglyme
1,2-dimethoxyethane
ethyl acetate
nitromethane

64.08
64.67
65.36
66.11
67.47
68.16
68.76
69.11
70.47
70.70
72.24
72.25
77.99
96.52
108.02
109.86
110.93
115.7
116.92
117.93
118.00
118.75
122.16
123.20
124.06
125.26
125.62
125.84
128.54
128.68
128.73
129.35

CH2
CH
CH2
CH2
CH2
CH2(2,5)
CH2
(CH3)3C
CH2
CH2
CH2
CH2
CH
CCl4
CH(3,4)
CH(3,4)
CH(3,5)
CH2
CN
CH(2,5)
CHCH2
CHCH2
CH(4,5)
CH2
CH(3,5)
CO2
CH(4)
CH(3,5)
CH(3,5)
CH
C(4)
CH(2,6)

ethylene glycol
2-propanol
allyl acetate
diethyl ether
1,4-dioxane
tetrahydrofuran
diallyl carbonate
tert-butyl alcohol
18-crown-6
diglyme
1,2-dimethoxyethane
diglyme
chloroform
carbon tetrachloride
pyrrole
furan
BHA
propylene
acetonitrile
pyrrole
allyl acetate
diallyl carbonate
imidazole
ethylene
pyridine
carbon dioxide
toluene
BHT
toluene
benzene
BHT
toluene

129.42
129.98
132.09
132.24
132.94
134.21
134.79
135.76
136.16
136.32
136.98
137.77
138.36
142.98
148.06
150.27
151.92
153.05
155.15
156.73
162.57
167.32
170.83
171.05
171.24
175.85
192.61
192.95
206.78
209.57
211.82

CH(3,5)
CH(2,6)
C
CHCH2
CHCH2
CH
CH (4)
CH(2)
CH(4)
C(2,6)
C(1)
C(4)
C(1)
CH(2,5)
C(2,6)
CH(2,6)
C(1)
C(1)
CO
CO
CH
CO2
CO
CO
CO
CO
HCO
CS2
CO
CO
CO

benzaldehyde
benzaldehyde
hexamethylbenzene
diallyl carbonate
allyl acetate
propylene
benzaldehyde
imidazole
pyridine
BHT
benzaldehyde
BHA
toluene
furan
BHA
pyridine
BHT
BHA
diallyl carbonate
dimethyl carbonate
dimethylformamide
dimethyl malonate
allyl acetate
dimethylacetamide
ethyl acetate
acetic acid
benzaldehyde
carbon disulfide
acetone
ethyl methyl ketone
cyclohexanone

S8

Table S7. CDCl3 (1H NMR data by chemical shift in ppm)


shift

mult

0.07
0.07
0.22
0.830.89
0.840.87
0.87
0.88
0.88
0.90
1.03
1.06
1.09
1.21
1.22
1.25
1.25
1.26
1.26
1.26
1.27
1.28
1.32
1.32
1.43
1.43
1.44
1.56
1.68
1.711.73
1.73
1.841.86
1.85
2.05
2.09
2.09
2.10
2.10

proton

s
CH3
s
CH3
s
CH4
m
CH3
m
CH3
s
CH3
t, 7
CH3
t, 7
CH3
t, 7.3
CH3
t, 7
CH3
t, 7
CH2CH3
s9
OH
t, 7
CH3
d, 6
CH3
t, 7
CH3
br s
CH2
t, 7
CH2CH3
m
CH2
br s
CH2
m
CH2
s
CH3
s6
OH
sept, 7.3
CH2
s
ArC(CH3)3
s
CH2
s
ArC(CH3)3
s
OH
m
CH2(3,4)
m
CH2(4)
dt, 6.4, 1.5
CH3
m
CH2(3,5)
m
CH2(3,4)
s
CH3CO
s
CH3
s
CH3CO
s
CH3
s
CH3

impurity

shift

mult

proton

impurity

shift

mult

proton

impurity

hexamethyldisiloxane
silicone grease
methane
pump oil
H grease8
ethane
n-hexane
n-pentane
propane
triethylamine
ethyl methyl ketone
methanol
diethyl ether
2-propanol
ethanol
H grease8
ethyl acetate
n-hexane
pump oil
n-pentane
tert-butyl alcohol
ethanol
propane
BHT
cyclohexane
BHA
water
pyrrolidine
cyclohexanone
propylene
cyclohexanone
tetrahydrofuran
ethyl acetate
allyl acetate
dimethylacetamide
acetic acid
acetonitrile

2.14
2.17
2.24
2.27
2.33
2.36
2.46
2.53
2.62
2.65
2.87
2.88
2.94
2.96
3.02
3.39
3.40
3.40
3.48
3.49
3.55
3.57
3.65
3.67
3.71
3.72
3.73
3.75
3.76
3.76
3.77
3.79
4.04
4.12
4.33
4.57
4.62

s
s
s
s
t
s
q, 7
q, 7
s
d, 9.5
m
s
s
s
s
s
s
s
q, 7
s9
s
m
m
s
s
q, 79
s
s
s
m
s
s
sept, 6
q, 7
s
ddd
s

CH3CO
CH3
CH3
ArCH3
CH2(2,6)
CH3
CH2CH3
CH2
CH3
CH3
CH2(2,5)
CH3
NCH3
CH3
NCH3
OCH3
CH3
CH2
CH2
CH3
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH3
CH2
CH2(2,5)
ArOCH3
CH3
CH
CH2CH3
CH3
CH2
H2

ethyl methyl ketone


acetone
hexamethylbenzene
BHT
cyclohexanone
toluene
ethyl methyl ketone
triethylamine
dimethyl sulfoxide
HMPA
pyrrolidine
dimethylformamide
dimethylacetamide
dimethylformamide
dimethylacetamide
diglyme
1,2-dimethoxyethane
dimethyl malonate
diethyl ether
methanol
1,2-dimethoxyethane
diglyme
diglyme
18-crown-6
1,4-dioxane
ethanol
1,2-dichloroethane
dimethyl malonate
ethylene glycol
tetrahydrofuran
BHA
dimethyl carbonate
2-propanol
ethyl acetate
nitromethane
allyl acetate
hydrogen

4.64
4.76
4.94
5.01
5.03
5.24
5.27
5.30
5.32
5.37
5.40
5.83
5.93
5.94
6.26
6.40
6.76
6.83
6.98
7.10
7.17
7.25
7.26
7.26
7.29
7.36
7.45
7.517.57
7.617.65
7.67
7.68
7.887.91
8.02
8.40
8.62
10.03

ddd
s
dm, 10
s
dm, 17
ddt
ddt
s
ddt
ddt
s
m
ddt
ddt
m
dd
s
m
s
s
m
m
s
s
m
s
dd
m
m
s
m
m
s
br t
m
s

CH2
OHd
CH2(1)
OHd
CH2(2)
CHCH2(2)
CHCH2(2)
CH2
CHCH2(1)
CHCH2(1)
CH2
CH
CHCH2
CHCH2
CH(3,4)
CH(3,4)
ArH
CH(2,5)
ArH
CH(4,5)
CH(2,4,6)
CH(3,5)
CH
CH
CH(3,5)
CH
CH(2,5)
CH(3,5)
CH(4)
CH(2)
CH(4)
CH(2,6)
CH
NH
CH(2,6)
HCO

diallyl carbonate
BHA
propylene
BHT
propylene
allyl acetate
diallyl carbonate
dichloromethane
allyl acetate
diallyl carbonate
ethylene
propylene
allyl acetate
diallyl carbonate
pyrrole
furan
BHA
pyrrole
BHT
imidazole
toluene
toluene
CDCl3 residual
chloroform
pyridine
benzene
furan
benzaldehyde
benzaldehyde
imidazole
pyridine
benzaldehyde
dimethylformamide
pyrrole
pyridine
benzaldehyde

Table S8. CDCl3 (13C{1H} NMR data by chemical shift in ppm)


shift

carbon

impurity

shift

carbon

impurity

shift

carbon

impurity

shift

carbon

impurity

4.63
1.19
1.89
1.97
6.89
7.86
11.61
14.08
14.14
14.19
15.20
16.37
16.63
16.98
18.41
19.50
20.81
21.02
21.04
21.20
21.46
21.53
22.38
22.70
24.97
25.14
25.56
25.62
26.94
27.00
29.49
29.71

CH4
CH3
CH3
CH3
CH3
CH2CH3
CH3
CH3
CH3
CH3
CH3
CH2
CH3
CH3
CH3
CH3
CH3
CH3
CH3CO
CH3Ar
CH3
CH3
CH2(2,4)
CH2(2,5)
CH2(4)
CH3
CH2(3,4)
CH2(3,4)
CH2
CH2(3,5)
CH3CO
CH2

methane
silicone grease
acetonitrile
hexamethyldisiloxane
ethane
ethyl methyl ketone
triethylamine
n-pentane
n-hexane
ethyl acetate
diethyl ether
propane
propane
hexamethylbenzene
ethanol
propylene
acetic acid
allyl acetate
ethyl acetate
BHT
toluene
dimethylacetamide
n-pentane
n-hexane
cyclohexanone
2-propanol
pyrrolidine
tetrahydrofuran
cyclohexane
cyclohexanone
ethyl methyl ketone
H grease8

29.84
30.32
30.33
30.92
31.25
31.45
31.64
34.16
34.25
34.72
35.28
36.50
36.87 (d)
36.89
38.13
40.76
41.11
41.97
43.50
46.25
46.93
50.41
52.57
53.52
54.89
55.70
58.28
59.01
59.08
60.49
62.50
63.79

CH2
(CH3)3C
(CH3)3C
CH3
(CH3)3C
CH3
CH2(3,4)
CH2(3)
(CH3)3C
(CH3)3C
NCH3
CH3
CH3
CH2CH3
NCH3
CH3
CH2
CH2(2,6)
CH2
CH2
CH2(2,5)
CH3
CH3
CH2
CH3
CH3O
CH2
CH3
CH3
CH2
CH3
CH2

pump oil
BHA
BHT
acetone
tert-butyl alcohol
dimethyl malonate
n-hexane
n-pentane
BHT
BHA
dimethylacetamide
dimethyl malonate
HMPAi
ethyl methyl ketone
dimethylacetamide
dimethyl sulfoxide
dimethyl malonate
cyclohexanone
1,2-dichloroethane
triethylamine
pyrrolidine
methanol
dimethyl malonate
dichloromethane
dimethyl carbonate
BHA
ethanol
diglyme
1,2-dimethoxyethane
ethyl acetate
nitromethane
ethylene glycol

64.50
65.28
65.91
67.14
67.97
68.55
69.15
70.51
70.55
71.84
71.90
77.16 (t)
77.36
96.34
107.98
109.57
110.69
115.74
116.43
117.77
118.34
118.96
122.00
123.13
123.75
124.99
125.33
125.55
128.26
128.27
128.37
129.07

CH
CH2
CH2
CH2
CH2(2,5)
CH2
(CH3)3C
CH2
CH2
CH2
CH2
CDCl3
CH
CCl4
CH(3,4)
CH(3,4)
CH(3,5)
CH2
CN
CH(2,5)
CHCH2
CHCH2
CH(4,5)
CH2
CH(3,5)
CO2
CH(4)
CH(3,5)
CH(3,5)
C(4)
CH
CH(2,6)

2-propanol
allyl acetate
diethyl ether
1,4-dioxane
tetrahydrofuran
diallyl carbonate
tert-butyl alcohol
diglyme
18-crown-6
1,2-dimethoxyethane
diglyme
CDCl3 signal
chloroform
carbon tetrachloride
pyrrole
furan
BHA
propylene
acetonitrile
pyrrole
allyl acetate
diallyl carbonate
imidazole
ethylene
pyridine
carbon dioxide
toluene
BHT
toluene
BHT
benzene
toluene

129.16
129.91
131.58
132.21
132.33
133.91
134.64
135.38
135.87
135.96
136.58
137.36
137.89
142.71
147.85
149.90
151.55
152.57
154.88
156.45
162.62
167.18
170.81
171.07
171.36
175.99
192.67
192.83
207.07
209.56
212.57

CH(3,5)
CH(2,6)
CHCH2
C
CHCH2
CH
CH (4)
CH(2)
C(2,6)
CH(4)
C(1)
C(4)
C(1)
CH(2,5)
C(2,6)
CH(2,6)
C(1)
C(1)
CO
CO
CH
CO2
CO
CO
CO
CO
HCO
CS2
CO
CO
CO

benzaldehyde
benzaldehyde
diallyl carbonate
hexamethylbenzene
allyl acetate
propylene
benzaldehyde
imidazole
BHT
pyridine
benzaldehyde
BHA
toluene
furan
BHA
pyridine
BHT
BHA
diallyl carbonate
dimethyl carbonate
dimethylformamide
dimethyl malonate
allyl acetate
dimethylacetamide
ethyl acetate
acetic acid
benzaldehyde
carbon disulfide
acetone
ethyl methyl ketone
cyclohexanone

S9

Table S9. Toluene-d8 (1H NMR data by chemical shift in ppm)


shift

mult

0.10
0.17
0.26
0.43
0.58
0.69
0.81
0.83
0.84
0.87
0.88
0.880.96
0.89
0.890.96
0.94
0.95
0.95
0.97
1.03
1.10
1.161.20
1.22
1.25
1.30
1.32
1.33
1.331.39
1.34
1.36
1.36
1.40
1.43
1.55
1.57
1.57
1.59
1.59
1.63

proton

s
CH3
s
CH4
s
CH3
s
OH
s
OH
s
CH3
s
CH3
s6
OH
t, 7
CH2CH3
t, 7
CH3
t, 7
CH3
m
CH3
t, 7.3
CH3
m
CH3
t, 7
CH2CH3
d, 6
CH3
t, 7
CH3
t, 7
CH3
s
CH3
t, 7
CH3
m
CH2(4)
m
CH2
m
CH2
br s
CH2
sept, 7.3
CH2
br s
CH2
m
CH2(3,5)
s
ArC(CH3)3
s
ArC(CH3)3
m
CH2(3,4)
s
CH2
m
CH2(3,4)
dt, 6.4, 1.5
CH3
s
CH3
s
CH3
s
CH3CO
s
CH3CO
s
CH3

impurity

shift

mult

proton

impurity

shift

mult

proton

impurity

hexamethyldisiloxane
methane
silicone grease
water
tert-butyl alcohol
acetonitrile
ethane
ethanol
ethyl methyl ketone
n-pentane
n-hexane
pump oil
propane
H grease8
ethyl acetate
2-propanol
triethylamine
ethanol
tert-butyl alcohol
diethyl ether
cyclohexanone
n-hexane
n-pentane
pump oil
propane
H grease8
cyclohexanone
BHA
BHT
pyrrolidine
cyclohexane
tetrahydrofuran
propylene
acetic acid
acetone
dimethylacetamide
ethyl methyl ketone
allyl acetate

1.64
1.69
1.82
1.95
1.96
2.08
2.10
2.11
2.11
2.23
2.37
2.39
2.42
2.54
2.56
2.91
2.92
3.01
3.03
3.12
3.12
3.24
3.25
3.31
3.31
3.31
3.33
3.36
3.36
3.36
3.43
3.48
3.54
3.65
3.87
4.32
4.34
4.34

s
s
q, 7
t
s
p
s
s
s
s
s
q, 7
d, 9.5
m
s
s
s
s
s9
s
s
s
q, 7
m
s
s
s
s
q, 76
s
m
s
m
sept, 6
q, 7
s
ddd
ddd

CH3
CH3CO
CH2CH3
CH2(2,6)
CH3
CH3
CH3
NCH3
CH3
ArCH3
CH3
CH2
CH3
CH2(2,5)
NCH3
CH2
CH2
CH3
CH3
OCH3
CH3
CH3
CH2
CH2
CH2
CH3
CH2
CH2
CH2
CH2
CH2
ArOCH3
CH2(2,5)
CH
CH2CH3
CH2
CH2
CH2

dimethyl sulfoxide
ethyl acetate
ethyl methyl ketone
cyclohexanone
dimethylformamide
Toluene-d8 residual
hexamethylbenzene
dimethylacetamide
toluene
BHT
dimethylformamide
triethylamine
HMPA
pyrrolidine
dimethylacetamide
1,2-dichloroethane
dimethyl malonate
nitromethane
methanol
diglyme
1,2-dimethoxyethane
dimethyl malonate
diethyl ether
diglyme
1,2-dimethoxyethane
dimethyl carbonate
1,4-dioxane
18-crown-6
ethanol
ethylene glycol
diglyme
BHA
tetrahydrofuran
2-propanol
ethyl acetate
dichloromethane
allyl acetate
diallyl carbonate

4.45
4.50
4.72
4.92
4.92
4.94
4.98
5.05
5.09
5.25
5.63
5.674
5.70
6.07
6.10
6.27
6.43
6.67
6.83
6.86
6.956.99
6.967.01
6.97
6.99
6.99
7.01
7.037.07
7.09
7.09
7.10
7.12
7.30
7.457.47
7.57
7.71
8.47
9.57

s
s
s
ddt
dm, 10
ddt
dm, 17
ddt
ddt
s
ddt
t(nfo ABX)
m
dd
s
m
m
m
s
s
m
m
p
s
m
s
m
m
m
dd
s
s
m
s
br t
m
s

OH5
H2
OH5
CHCH2(2)
CH2(1)
CHCH2(2)
CH2(2)
CHCH2(1)
CHCH2(1)
CH2
CHCH2
CHCH2
CH
CH(3,4)
CH
CH(3,4)
CH(2,5)
CH(3,5)
ArH
CH(4,5)
CH(3,5)
CH(2,4,6)
CH(4)
ArH
CH(4)
CH(2,6)
CH(4)
CH(3,5)
CH(3,5)
CH(2,5)
CH
CH(2)
CH(2,6)
CH
NH
CH(2,6)
HCO

BHA
hydrogen
BHT
diallyl carbonate
propylene
allyl acetate
propylene
allyl acetate
diallyl carbonate
ethylene
diallyl carbonate
allyl acetate
propylene
furan
chloroform
pyrrole
pyrrole
pyridine
BHA
imidazole
benzaldehyde
toluene
Toluene-d8 residual
BHT
pyridine
Toluene-d8 residual
benzaldehyde
Toluene-d8 residual
toluene
furan
benzene
imidazole
benzaldehyde
dimethylformamide
pyrrole
pyridine
benzaldehyde

Table S10. Toluene-d8 (13C{1H} NMR data by chemical shift in ppm)


shift

carbon

impurity

shift

carbon

impurity

shift

carbon

impurity

shift

carbon

impurity

4.34
0.03
1.37
1.99
6.94
7.89
12.39
14.23
14.27
14.34
15.47
16.63
16.65
16.84
18.78
19.32
20.21
20.27
20.43 (sept)
20.46
21.05
21.37
21.42
22.79
23.12
25.15
25.24
25.75
25.79
27.05
27.31
28.74
30.03

CH4
CH3
CH3
CH3
CH3
CH2CH3
CH3
CH3
CH3
CH3
CH3
CH2
CH3
CH3
CH3
CH3
CH3
CH3
CD3
CH3CO
CH3
CH3
CH3Ar
CH2(2,4)
CH2(2,5)
CH2(4)
CH3
CH2(3,4)
CH2(3,4)
CH2(3,5)
CH2
CH3CO
CH3

methane
acetonitrile
silicone grease
hexamethyldisiloxane
ethane
ethyl methyl ketone
triethylamine
ethyl acetate
n-pentane
n-hexane
diethyl ether
propane
propane
hexamethylbenzene
ethanol
propylene
allyl acetate
acetic acid
toluene-d8 signal
ethyl acetate
dimethylacetamide
toluene
BHT
n-pentane
n-hexane
cyclohexanone
2-propanol
pyrrolidine
tetrahydrofuran
cyclohexanone
cyclohexane
ethyl methyl ketone
acetone

30.30
30.31
30.33
30.49
30.64
31.39
32.06
34.39
34.54
34.58
34.69
35.22
36.32
36.8 (d)
36.98
40.41
40.88
41.78
43.40
46.82
47.12
49.90
51.76
53.47
54.13
55.04
57.81
58.62
58.63
60.08
61.14
64.12
64.29

(CH3)3C
CH2
CH2
(CH3)3C
CH3
(CH3)3C
CH2(3,4)
(CH3)3C
CH2(3)
NCH3
(CH3)3C
CH3
CH2CH3
CH3
NCH3
CH3
CH2
CH2(2,6)
CH2
CH2
CH2(2,5)
CH3
CH3
CH2
CH3
CH3O
CH2
CH3
CH3
CH2
CH3
CH
CH2

BHA
H grease8
pump oil
tert-butyl alcohol
dimethylformamide
BHT
n-hexane
BHT
n-pentane
dimethylacetamide
BHA
dimethylformamide
ethyl methyl ketone
HMPA11
dimethylacetamide
dimethyl sulfoxide
dimethyl malonate
cyclohexanone
1,2-dichloroethane
triethylamine
pyrrolidine
methanol
dimethyl malonate
dichloromethane
dimethyl carbonate
BHA
ethanol
diglyme
1,2-dimethoxyethane
ethyl acetate
nitromethane
2-propanol
ethylene glycol

64.87
65.94
67.17
67.75
68.12
68.20
70.86
70.92
72.25
72.39
77.89
96.57
108.15
109.63
110.99
115.76
115.89
117.49
117.61
118.04
122.13
122.92
123.46
124.86
125.13 (t)
125.66
125.79
127.96 (t)
128.44
128.51
128.57
128.68
128.87 (t)

CH2
CH2
CH2
CH2(2,5)
(CH3)3C
CH2
CH2
CH2
CH2
CH2
CH
CCl4
CH(3,4)
CH(3,4)
CH(3,5)
CN
CH2
CHCH2
CH(2,5)
CHCH2
CH(4,5)
CH2
CH(3,5)
CO2
CD(4)
CH(4)
CH(3,5)
CD(3,5)
C(4)
CH(3,5)
CH
CH(3,5)
CD(2,6)

allyl acetate
diethyl ether
1,4-dioxane
tetrahydrofuran
tert-butyl alcohol
diallyl carbonate
18-crown-6
diglyme
1,2-dimethoxyethane
diglyme
chloroform
carbon tetrachloride
pyrrole
furan
BHA
acetonitrile
propylene
allyl acetate
pyrrole
diallyl carbonate
imidazole
ethylene
pyridine
carbon dioxide
toluene-d8 signal
toluene
BHT
toluene-d8 signal
BHT
toluene
benzene
benzaldehyde
toluene-d8 signal

129.33
129.61
131.72
132.30
132.98
133.61
133.88
135.17
135.57
136.12
137.12
137.34
137.48
137.84
142.65
148.06
150.25
152.06
153.50
155.15
156.61
161.93
166.49
169.44
169.65
170.02
175.30
191.09
192.71
204.00
206.31
208.60

CH(2,6)
CH(2,6)
C
CHCH2
CHCH2
CH
CH (4)
CH(4)
CH(2)
C(2,6)
C(1)
C(4)
C
C(1)
CH(2,5)
C(2,6)
CH(2,6)
C(1)
C(1)
CO
CO
CH
CO2
CO
CO
CO
CO
HCO
CS2
CO
CO
CO

toluene
benzaldehyde
hexamethylbenzene
diallyl carbonate
allyl acetate
propylene
benzaldehyde
pyridine
imidazole
BHT
benzaldehyde
BHA
toluene-d8 signal
toluene
furan
BHA
pyridine
BHT
BHA
diallyl carbonate
dimethyl carbonate
dimethylformamide
dimethyl malonate
allyl acetate
dimethylacetamide
ethyl acetate
acetic acid
benzaldehyde
carbon disulfide
acetone
ethyl methyl ketone
cyclohexanone

S10

Table S11. C6D6 (1H NMR data by chemical shift in ppm)


shift

mult

0.12
0.16
0.29
0.40
0.50
0.58
0.63
0.80
0.85
0.86
0.87
0.89
0.900.98
0.910.97
0.92
0.95
0.96
0.96
1.05
1.081.16
1.11
1.23
1.24
1.26
1.281.37
1.32
1.33
1.37
1.38
1.40
1.40
1.41
1.52
1.55
1.55
1.58
1.60

proton

s
CH3
s
CH4
s
CH3
s
OH
6
s
OH
s
CH3
s
OH
s
CH3
t, 7
CH2CH3
t, 7.3
CH3
t, 7
CH3
t, 7
CH3
m
CH3
m
CH3
t, 7
CH2CH3
d, 6
CH3
t, 7
CH3
t, 7
CH3
s
CH3
m
CH2(4)
t, 7
CH3
m
CH2
m
CH2
sept, 7.3
CH2
m
CH2(3,5)
br s
CH2
m
CH2(3,4)
br s
CH2
s
ArC(CH3)3
s
CH2
m
CH2(3,4)
s
ArC(CH3)3
s
CH3
s
CH3
dt, 6.4, 1.5
CH3
s
CH3CO
s
CH3CO

impurity

shift

mult

proton

impurity

shift

mult

proton

impurity

hexamethyldisiloxane
methane
silicone grease
water
ethanol
acetonitrile
tert-butyl alcohol
ethane
ethyl methyl ketone
propane
n-pentane
n-hexane
H grease8
pump oil
ethyl acetate
2-propanol
ethanol
triethylamine
tert-butyl alcohol
cyclohexanone
diethyl ether
n-pentane
n-hexane
propane
cyclohexanone
H grease8
pyrrolidine
pump oil
BHT
cyclohexane
tetrahydrofuran
BHA
acetic acid
acetone
propylene
ethyl methyl ketone
dimethylacetamide

1.63
1.65
1.68
1.81
1.86
1.98
2.05
2.11
2.13
2.24
2.36
2.40
2.40
2.54
2.57
2.90
2.94
2.97
3.07
3.11
3.12
3.23
3.26
3.30
3.33
3.34
3.34
3.35
3.39
3.41
3.46
3.48
3.57
3.67
3.89
4.27
4.38

s
s
s
q, 7
s
t
s
s
s
s
s
d, 9.5
q, 7
m
s
s
s
s
s9
s
s
s
q, 7
s
s
m
q, 76
s
s
s
m
s
m
sept, 6
q, 7
s
ddd

CH3
CH3CO
CH3
CH2CH3
CH3
CH2(2,6)
NCH3
CH3
CH3
ArCH3
CH3
CH3
CH2
CH2(2,5)
NCH3
CH2
CH3
CH2
CH3
OCH3
CH3
CH3
CH2
CH3
CH2
CH2
CH2
CH2
CH2
CH2
CH2
ArOCH3
CH2(2,5)
CH
CH2CH3
CH2
CH2

allyl acetate
ethyl acetate
dimethyl sulfoxide
ethyl methyl ketone
dimethylformamide
cyclohexanone
dimethylacetamide
toluene
hexamethylbenzene
BHT
dimethylformamide
HMPA
triethylamine
pyrrolidine
dimethylacetamide
1,2-dichloroethane
nitromethane
dimethyl malonate
methanol
diglyme
1,2-dimethoxyethane
dimethyl malonate
diethyl ether
dimethyl carbonate
1,2-dimethoxyethane
diglyme
ethanol
1,4-dioxane
18-crown-6
ethylene glycol
diglyme
BHA
tetrahydrofuran
2-propanol
ethyl acetate
dichloromethane
allyl acetate

4.38
4.47
4.53
4.79
4.92
4.94
4.95
5.01
5.06
5.09
5.25
5.65
5.684
5.72
6.08
6.15
6.37
6.48
6.66
6.90
6.93
6.936.99
6.98
7.017.07
7.02
7.05
7.13
7.13
7.15
7.16
7.33
7.497.53
7.63
7.80
8.53
9.64

ddd
s
s
s
ddt
ddt
dm, 10
dm, 17
ddt
ddt
s
ddt
t(nfo ABX)
m
dd
s
m
m
m
s
s
m
m
m
m
s
dd
m
s
s
s
m
s
br t
m
s

CH2
H2
OH5
OH5
CHCH2(2)
CHCH2(2)
CH2(1)
CH2(2)
CHCH2(1)
CHCH2(1)
CH2
CHCH2
CHCH2
CH
CH(3,4)
CH
CH(3,4)
CH(2,5)
CH(3,5)
CH(4,5)
ArH
CH(3,5)
CH(4)
CH(4)
CH(2,4,6)
ArH
CH(2,5)
CH(3,5)
CH
CH
CH(2)
CH(2,6)
CH
NH
CH(2,6)
HCO

diallyl carbonate
hydrogen
BHA
BHT
diallyl carbonate
allyl acetate
propylene
propylene
allyl acetate
diallyl carbonate
ethylene
diallyl carbonate
allyl acetate
propylene
furan
chloroform
pyrrole
pyrrole
pyridine
imidazole
BHA
benzaldehyde
pyridine
benzaldehyde
toluene
BHT
furan
toluene
benzene
C6D6 residual
imidazole
benzaldehyde
dimethylformamide
pyrrole
pyridine
benzaldehyde

Table S12. C6D6 (13C{1H} NMR data by chemical shift in ppm)


shift

carbon

impurity

shift

carbon

impurity

shift

carbon

impurity

shift

carbon

impurity

4.29
0.20
1.38
2.05
6.96
7.91
12.35
14.19
14.25
14.32
15.46
16.60
16.66
16.95
18.72
19.38
20.37
20.37
20.56
21.10
21.16
21.40
22.72
23.04
25.03
25.18
25.65
25.72
27.00
27.23
28.56
30.14

CH4
CH3
CH3
CH3
CH3
CH2CH3
CH3
CH3
CH3
CH3
CH3
CH2
CH3
CH3
CH3
CH3
CH3
CH3
CH3CO
CH3
CH3
CH3Ar
CH2(2,4)
CH2(2,5)
CH2(4)
CH3
CH2(3,4)
CH2(3,4)
CH2(3,5)
CH2
CH3CO
CH3

methane
acetonitrile
silicone grease
hexamethyldisiloxane
ethane
ethyl methyl ketone
triethylamine
ethyl acetate
n-pentane
n-hexane
diethyl ether
propane
propane
hexamethylbenzene
ethanol
propylene
acetic acid
allyl acetate
ethyl acetate
toluene
dimethylacetamide
BHT
n-pentane
n-hexane
cyclohexanone
2-propanol
pyrrolidine
tetrahydrofuran
cyclohexanone
cyclohexane
ethyl methyl ketone
acetone

30.22
30.24
30.35
30.47
30.72
31.34
31.96
34.35
34.45
34.67
34.72
35.25
36.36
36.88 (d)
37.03
40.03
41.04
41.83
43.59
46.77
46.86
49.97
51.86
53.46
54.30
55.27
57.86
58.66
58.68
60.21
61.16
64.23

CH2
CH2
(CH3)3C
(CH3)3C
CH3
(CH3)3C
CH2(3,4)
(CH3)3C
CH2(3)
NCH3
(CH3)3C
CH3
CH2CH3
CH3
NCH3
CH3
CH2
CH2(2,6)
CH2
CH2
CH2(2,5)
CH3
CH3
CH2
CH3
CH3O
CH2
CH3
CH3
CH2
CH3
CH

H grease8
pump oil
BHA
tert-butyl alcohol
dimethylformamide
BHT
n-hexane
BHT
n-pentane
dimethylacetamide
BHA
dimethylformamide
ethyl methyl ketone
HMPA11
dimethylacetamide
dimethyl sulfoxide
dimethyl malonate
cyclohexanone
1,2-dichloroethane
triethylamine
pyrrolidine
methanol
dimethyl malonate
dichloromethane
dimethyl carbonate
BHA
ethanol
diglyme
1,2-dimethoxyethane
ethyl acetate
nitromethane
2-propanol

64.34
64.92
65.94
67.16
67.80
68.19
68.28
70.59
70.87
72.21
72.35
77.79
96.44
108.21
109.67
111.15
115.92
116.02
117.64
117.78
118.22
122.16
122.96
123.58
124.76
125.68
125.83
128.06 (t)
128.52
128.56
128.62
128.95

CH2
CH2
CH2
CH2
CH2(2,5)
(CH3)3C
CH2
CH2
CH2
CH2
CH2
CH
CCl4
CH(3,4)
CH(3,4)
CH(3,5)
CH2
CN
CHCH2
CH(2,5)
CHCH2
CH(4,5)
CH2
CH(3,5)
CO2
CH(4)
CH(3,5)
CD
C(4)
CH(3,5)
CH
CH(3,5)

ethylene glycol
allyl acetate
diethyl ether
1,4-dioxane
tetrahydrofuran
tert-butyl alcohol
diallyl carbonate
18-crown-6
diglyme
1,2-dimethoxyethane
diglyme
chloroform
carbon tetrachloride
pyrrole
furan
BHA
propylene
acetonitrile
allyl acetate
pyrrole
diallyl carbonate
imidazole
ethylene
pyridine
carbon dioxide
toluene
BHT
C6D6 signal
BHT
toluene
benzene
benzaldehyde

129.33
129.65
131.79
132.18
132.90
133.69
133.95
135.28
135.76
136.08
137.05
137.50
137.91
142.73
148.13
150.27
152.05
153.62
155.24
156.71
162.13
166.66
169.67
169.95
170.44
175.82
191.43
192.69
204.43
206.55
209.10

CH(2,6)
CH(2,6)
C
CHCH2
CHCH2
CH
CH (4)
CH(4)
CH(2)
C(2,6)
C(1)
C(4)
C(1)
CH(2,5)
C(2,6)
CH(2,6)
C(1)
C(1)
CO
CO
CH
CO2
CO
CO
CO
CO
HCO
CS2
CO
CO
CO

toluene
benzaldehyde
hexamethylbenzene
diallyl carbonate
allyl acetate
propylene
benzaldehyde
pyridine
imidazole
BHT
benzaldehyde
BHA
toluene
furan
BHA
pyridine
BHT
BHA
diallyl carbonate
dimethyl carbonate
dimethylformamide
dimethyl malonate
allyl acetate
dimethylacetamide
ethyl acetate
acetic acid
benzaldehyde
carbon disulfide
acetone
ethyl methyl ketone
cyclohexanone

S11

Table S13. C6D5Cl (1H NMR data by chemical shift in ppm)


shift

mult

0.10
0.14
0.15
0.79
0.84
0.84
0.85
0.860.92
0.880.91
0.89
0.93
1.03
1.04
1.04
1.06
1.10
1.12
1.19
1.21
1.23
1.26
1.30
1.30
1.30
1.31
1.331.37
1.37
1.37
1.37
1.39
1.43
1.481.53
1.55
1.58
1.74
1.76
1.77
1.78

proton

s
CH3
s
CH3
s
CH4
s
CH3
t, 7
CH3
t, 7.3
CH3
t, 7
CH3
m
CH3
m
CH3
t, 7
CH2CH3
t, 7
CH3
s
OH
t, 7
CH2CH3
d, 6
CH3
t, 7
CH3
t, 7
CH3
s
CH3
m
CH2
s
CH3
m
CH2
sept, 7.3
CH2
s
OH
br s
CH2
9
s
OH
br s
CH2
m
CH2(4)
s
ArC(CH3)3
s
ArC(CH3)3
s
CH2
6
s
OH
m
CH2(3,4)
m
CH2(3,5)
m
CH2(3,4)
dt, 6.4, 1.5
CH3
s
CH3CO
s
CH3
s
CH3
s
CH3CO

impurity

shift

mult

proton

impurity

shift

mult

proton

impurity

hexamethyldisiloxane
silicone grease
methane
ethane
n-pentane
propane
n-hexane
H grease8
pump oil
ethyl methyl ketone
triethylamine
water
ethyl acetate
2-propanol
ethanol
diethyl ether
tert-butyl alcohol
n-hexane
acetonitrile
n-pentane
propane
tert-butyl alcohol
H grease8
methanol
pump oil
cyclohexanone
BHA
BHT
cyclohexane
ethanol
pyrrolidine
cyclohexanone
tetrahydrofuran
propylene
dimethylacetamide
acetic acid
acetone
ethyl acetate

1.78
1.80
2.03
2.06
2.08
2.10
2.16
2.20
2.30
2.39
2.42
2.47
2.51
2.64
2.65
3.15
3.16
3.17
3.25
3.26
3.31
3.37
3.37
3.41
3.41
3.45
3.48
3.49
3.51
3.58
3.59
3.59
3.61
3.82
3.96
4.44
4.46
4.49

s
s
s
q, 7
t
s
s
s
s
q, 7
s
d, 9.5
s
m
s
s
s
s
s9
s
q, 7
m
s
s
s
s
s
m
q, 76
s
s
m
s
sept, 6
q, 7
ddd
ddd
s

CH3CO
CH3
CH3
CH2CH3
CH2(2,6)
CH3
CH3
ArCH3
CH3
CH2
NCH3
CH3
CH3
CH2(2,5)
NCH3
CH2
OCH3
CH3
CH3
CH2
CH2
CH2
CH2
CH2
CH3
CH2
CH3
CH2
CH2
CH2
CH3
CH2(2,5)
ArOCH3
CH
CH2CH3
CH2
CH2
H2

ethyl methyl ketone


allyl acetate
dimethyl sulfoxide
ethyl methyl ketone
cyclohexanone
hexamethylbenzene
toluene
BHT
dimethylformamide
triethylamine
dimethylacetamide
HMPA
dimethylformamide
pyrrolidine
dimethylacetamide
dimethyl malonate
diglyme
1,2-dimethoxyethane
methanol
1,2-dichloroethane
diethyl ether
diglyme
1,2-dimethoxyethane
18-crown-6
dimethyl malonate
1,4-dioxane
dimethyl carbonate
diglyme
ethanol
ethylene glycol
nitromethane
tetrahydrofuran
BHA
2-propanol
ethyl acetate
allyl acetate
diallyl carbonate
hydrogen

4.62
4.77
4.91
4.98
5.03
5.04
5.15
5.17
5.29
5.50
5.72
5.75
5.77
6.19
6.27
6.62
6.74
6.83
6.90
6.96
6.97
6.99
7.01
7.017.08
7.107.17
7.14
7.157.19
7.20
7.24
7.247.28
7.25
7.53
7.597.61
7.73
8.51
8.61
9.77

s
s
dm, 10
dm, 17
ddt
ddt
ddt
ddt
s
s
m
ddt
ddt
dd
m
m
s
s
m
br. s
s
br. s
s
m
m
br. s
m
s
dd
m
m
s
m
s
m
br t
s

OH5
CH2
CH2(1)
CH2(2)
CHCH2(2)
CHCH2(2)
CHCH2(1)
CHCH2(1)
CH2
OH5
CH
CHCH2
CHCH2
CH(3,4)
CH(3,4)
CH(2,5)
CH
ArH
CH(3,5)
CH(4)
ArH
CH(3,5)
CH(4,5)
CH(2,4,6)
CH(3,5)
CH(2,6)
CH(3,5)
CH
CH(2,5)
CH(4)
CH(4)
CH(2)
CH(2,6)
CH
CH(2,6)
NH
HCO

BHA
dichloromethane
propylene
propylene
diallyl carbonate
allyl acetate
allyl acetate
diallyl carbonate
ethylene
BHT
propylene
diallyl carbonate
allyl acetate
furan
pyrrole
pyrrole
chloroform
BHA
pyridine
C6D5Cl residual
BHT
C6D5Cl residual
imidazole
toluene
toluene
C6D5Cl residual
benzaldehyde
benzene
furan
benzaldehyde
pyridine
imidazole
benzaldehyde
dimethylformamide
pyridine
pyrrole
benzaldehyde

Table S14. C6D5Cl (13C{1H} NMR data by chemical shift in ppm)


shift

carbon

impurity

shift

carbon

impurity

shift

carbon

impurity

shift

carbon

impurity

4.33
0.63
1.09
1.92
6.91
7.79
11.87
14.07
14.10
14.18
15.35
16.48
16.56
16.68
18.55
19.32
20.40
20.40
20.50
21.03
21.10
21.23
22.54
22.86
25.07
25.14
25.59
25.68
26.99
27.02
28.82
30.11
30.11

CH4
CH3
CH3
CH3
CH3
CH2CH3
CH3
CH3
CH3
CH3
CH3
CH2
CH3
CH3
CH3
CH3
CH3
CH3
CH3CO
CH3
CH3Ar
CH3
CH2(2,4)
CH2(2,5)
CH2(4)
CH3
CH2(3,4)
CH2(3,4)
CH2
CH2(3,5)
CH3CO
CH2
CH2

methane
acetonitrile
silicone grease
hexamethyldisiloxane
ethane
ethyl methyl ketone
triethylamine
ethyl acetate
n-pentane
n-hexane
diethyl ether
propane
propane
hexamethylbenzene
ethanol
propylene
acetic acid
allyl acetate
ethyl acetate
dimethylacetamide
BHT
toluene
n-pentane
n-hexane
cyclohexanone
2-propanol
pyrrolidine
tetrahydrofuran
cyclohexane
cyclohexanone
ethyl methyl ketone
H grease8
pump oil

30.12
30.19
30.21
30.71
31.13
31.77
34.11
34.26
34.56
34.59
35.45
36.39
36.64 (d)
37.13
40.27
40.93
41.79
43.60
46.36
46.75
49.66
51.89
53.54
54.23
55.08
57.63
58.31
58.42
60.06
61.68
64.03
64.18
64.86

CH3
(CH3)3C
(CH3)3C
CH3
(CH3)3C
CH2(3,4)
(CH3)3C
CH2(3)
(CH3)3C
NCH3
CH3
CH2CH3
CH3
NCH3
CH3
CH2
CH2(2,6)
CH2
CH2
CH2(2,5)
CH3
CH3
CH2
CH3
CH3O
CH2
CH3
CH3
CH2
CH3
CH2
CH
CH2

acetone
BHT
BHA
dimethylformamide
tert-butyl alcohol
n-hexane
BHT
n-pentane
BHA
dimethylacetamide
dimethylformamide
ethyl methyl ketone
HMPA11
dimethylacetamide
dimethyl sulfoxide
dimethyl malonate
cyclohexanone
1,2-dichloroethane
triethylamine
pyrrolidine
methanol
dimethyl malonate
dichloromethane
dimethyl carbonate
BHA
ethanol
1,2-dimethoxyethane
diglyme
ethyl acetate
nitromethane
ethylene glycol
2-propanol
allyl acetate

65.79
66.95
67.64
68.19
68.19
70.55
70.56
71.81
72.07
77.67
96.38
108.03
109.64
110.84
115.86
115.93
117.63
117.65
118.22
121.96
122.95
123.49
125.43
125.58
125.96 (t)
126.08
128.25 (t)
128.26
128.31
128.38
128.87
129.12

CH2
CH2
CH2(2,5)
(CH3)3C
CH2
CH2
CH2
CH2
CH2
CH
CCl4
CH(3,4)
CH(3,4)
CH(3,5)
CH2
CN
CHCH2
CH(2,5)
CHCH2
CH(4,5)
CH2
CH(3,5)
CH(4)
CH(3,5)
CD(4)
CO2
CD(3,5)
C(4)
CH(3,5)
CH
CH(3,5)
CH(2,6)

diethyl ether
1,4-dioxane
tetrahydrofuran
tert-butyl alcohol
diallyl carbonate
18-crown-6
diglyme
1,2-dimethoxyethane
diglyme
chloroform
carbon tetrachloride
pyrrole
furan
BHA
propylene
acetonitrile
allyl acetate
pyrrole
diallyl carbonate
imidazole
ethylene
pyridine
toluene
BHT
C6D5Cl signal
carbon dioxide
C6D5Cl signal
BHT
toluene
benzene
benzaldehyde
toluene

129.26 (t)
129.49
131.54
131.93
132.69
133.57
134.02
134.19
135.32
135.50
135.92
136.78
137.29
137.65
142.49
147.87
149.93
151.69
153.19
154.87
156.36
162.01
166.51
169.59
169.79
170.20
175.67
191.24
192.49
204.83
206.87
209.30

CD(2,6)
CH(2,6)
C
CHCH2
CHCH2
CH
CH (4)
CCl
CH(4)
CH(2)
C(2,6)
C(1)
C(4)
C(1)
CH(2,5)
C(2,6)
CH(2,6)
C(1)
C(1)
CO
CO
CH
CO2
CO
CO
CO
CO
HCO
CS2
CO
CO
CO

C6D5Cl signal
benzaldehyde
hexamethylbenzene
diallyl carbonate
allyl acetate
propylene
benzaldehyde
C6D5Cl signal
pyridine
imidazole
BHT
benzaldehyde
BHA
toluene
furan
BHA
pyridine
BHT
BHA
diallyl carbonate
dimethyl carbonate
dimethylformamide
dimethyl malonate
allyl acetate
dimethylacetamide
ethyl acetate
acetic acid
benzaldehyde
carbon disulfide
acetone
ethyl methyl ketone
cyclohexanone

S12

Table S15. (CD3)2CO (1H NMR data by chemical shift in ppm)


shift

mult

0.07
0.13
0.17
0.83
0.87
0.88
0.88
0.88
0.90
0.96
0.96
1.10
1.11
1.12
1.18
1.20
1.27
1.28
1.29
1.29
1.31
1.41
1.41
1.43
1.68
1.701.74
1.79
1.791.83
1.96
1.97
1.97
2.02
2.05
2.05
2.07
2.09

proton

s
CH3
s
CH3
s
CH4
s
CH3
m
CH3
t, 7
CH3
t, 7
CH3
t, 7.3
CH3
m
CH3
t, 7
CH2CH3
t, 7
CH3
d, 6
CH3
t, 7
CH3
t, 7
CH3
s
CH3
t, 7
CH2CH3
m
CH2
m
CH2
br s
CH2
br s
CH2
sept, 7.3
CH2
s
ArC(CH3)3
s
ArC(CH3)3
s
CH2
dt, 6.4, 1.5
CH3
m
CH2(4)
m
CH2(3,4)
m
CH2(3,5)
s
CH3
s
CH3CO
s
CH3CO
s
CH3
s
CH3
p
CHD2
s
CH3CO
s
CH3

impurity

shift

mult

proton

impurity

shift

mult

proton

impurity

hexamethyldisiloxane
silicone grease
methane
ethane
pump oil
n-hexane
n-pentane
propane
H grease8
ethyl methyl ketone
triethylamine
2-propanol
diethyl ether
ethanol
tert-butyl alcohol
ethyl acetate
n-pentane
n-hexane
H grease8
pump oil
propane
BHA
BHT
cyclohexane
propylene
cyclohexanone
tetrahydrofuran
cyclohexanone
acetic acid
dimethylacetamide
ethyl acetate
allyl acetate
acetonitrile
(CD3)2CO residual
ethyl methyl ketone
acetone

2.17
2.22
2.27
2.32
2.45
2.45
2.52
2.59
2.78
2.83
2.843
2.94
3.00
3.12
3.28
3.28
3.28
3.31
3.39
3.41
3.42
3.46
3.47
3.56
3.57
3.59
3.59
3.63
3.68
3.72
3.72
3.87
3.90
4.05
4.43
4.53

s
s
t
s
q, 7
q, 7
s
d, 9.5
s
s
s
s
s
s9
s
s
s
s9
s6
q, 7
s
s
m
m
q, 76
s
s
m
s
s
s
s
sept, 6
q, 7
s
ddd

CH3
ArCH3
CH2(2,6)
CH3
CH2CH3
CH2
CH3
CH3
CH3
NCH3
OH
CH3
NCH3
OH
OCH3
CH3
CH2
CH3
OH
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2(2,5)
CH3
ArOCH3
CH3
CH2
CH
CH2CH3
CH3
CH2

hexamethylbenzene
BHT
cyclohexanone
toluene
ethyl methyl ketone
triethylamine
dimethyl sulfoxide
HMPA
dimethylformamide
dimethylacetamide
water
dimethylformamide
dimethylacetamide
methanol
diglyme
1,2-dimethoxyethane
ethylene glycol
methanol
ethanol
diethyl ether
dimethyl malonate
1,2-dimethoxyethane
diglyme
diglyme
ethanol
18-crown-6
1,4-dioxane
tetrahydrofuran
dimethyl malonate
BHA
dimethyl carbonate
1,2-dichloroethane
2-propanol
ethyl acetate
nitromethane
allyl acetate

4.54
4.62
4.90
5.00
5.18
5.23
5.29
5.35
5.38
5.63
5.65
5.81
5.92
5.96
6.07
6.43
6.72
6.77
6.96
7.04
7.107.20
7.107.20
7.35
7.36
7.56
7.597.63
7.62
7.697.73
7.76
7.927.94
7.96
8.02
8.58
10.02
10.05

s
ddd
dm, 10
dm, 17
ddt
ddt
ddt
ddt
s
s
s
m
ddt
ddt
m
dd
s
m
s
s
m
m
m
s
dd
m
s
m
m
m
s
s
m
br t
s

H2
CH2
CH2(1)
CH2(2)
CHCH2(2)
CHCH2(2)
CHCH2(1)
CHCH2(1)
CH2
CH2
OH5
CH
CHCH2
CHCH2
CH(3,4)
CH(3,4)
ArH
CH(2,5)
ArH
CH(4,5)
CH(2,4,6)
CH(3,5)
CH(3,5)
CH
CH(2,5)
CH(3,5)
CH(2)
CH(4)
CH(4)
CH(2,6)
CH
CH
CH(2,6)
NH
HCO

hydrogen
diallyl carbonate
propylene
propylene
allyl acetate
diallyl carbonate
allyl acetate
diallyl carbonate
ethylene
dichloromethane
BHA
propylene
allyl acetate
diallyl carbonate
pyrrole
furan
BHA
pyrrole
BHT
imidazole
toluene
toluene
pyridine
benzene
furan
benzaldehyde
imidazole
benzaldehyde
pyridine
benzaldehyde
dimethylformamide
chloroform
pyridine
pyrrole
benzaldehyde

Table S16. (CD3)2CO (13C{1H} NMR data by chemical shift in ppm)


shift

carbon

impurity

shift

carbon

impurity

shift

carbon

impurity

shift

carbon

impurity

5.33
1.12
1.40
2.01
6.88
8.03
12.49
14.29
14.34
14.50
15.78
16.68
16.78
16.86
18.89
19.42
20.51
20.68
20.83
21.31
21.46
21.51
22.98
23.28
25.59
25.67
26.15
27.51
27.68
29.30
29.84 (sept)
30.36

CH4
CH3
CH3
CH3
CH3
CH2CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH2
CH3
CH3
CH3
CH3
CH3
CH3CO
CH3Ar
CH3
CH3
CH2(2,4)
CH2(2,5)
CH2(4)
CH3
CH2(3,4)
CH2
CH2(3,5)
CH3CO
CD3
CH2

methane
acetonitrile
silicone grease
hexamethyldisiloxane
ethane
ethyl methyl ketone
triethylamine
n-pentane
n-hexane
ethyl acetate
diethyl ether
propane
propane
hexamethylbenzene
ethanol
propylene
acetic acid
allyl acetate
ethyl acetate
BHT
toluene
dimethylacetamide
n-pentane
n-hexane
cyclohexanone
2-propanol
tetrahydrofuran
cyclohexane
cyclohexanone
ethyl methyl ketone
(CD3)2CO signal
pump oil

30.60
30.64
30.72
31.03
31.61
32.30
34.83
34.89
35.00
35.45
36.15
36.75
37.04 (d)
37.92
41.23
41.43
42.24
45.25
47.07
49.77
52.47
54.95
54.95
55.51
57.72
58.45
58.77
60.56
63.21
63.85
64.26

CH3
(CH3)3C
(CH3)3C
CH3
(CH3)3C
CH2(3,4)
CH2(3)
NCH3
(CH3)3C
(CH3)3C
CH3
CH2CH3
CH3
NCH3
CH3
CH2
CH2(2,6)
CH2
CH2
CH3
CH3
CH2
CH3
CH3O
CH2
CH3
CH3
CH2
CH3
CH
CH2

acetone
BHA
tert-butyl alcohol
dimethylformamide
BHT
n-hexane
n-pentane
dimethylacetamide
BHT
BHA
dimethylformamide
ethyl methyl ketone
HMPA11
dimethylacetamide
dimethyl sulfoxide
dimethyl malonate
cyclohexanone
1,2-dichloroethane
triethylamine
methanol
dimethyl malonate
dichloromethane
dimethyl carbonate
BHA
ethanol
1,2-dimethoxyethane
diglyme
ethyl acetate
nitromethane
2-propanol
ethylene glycol

65.28
66.12
67.60
68.07
68.13
68.78
71.03
71.25
72.47
72.63
79.19
96.65
108.04
110.24
111.00
116.03
117.60
117.81
117.98
118.53
122.31
123.47
124.57
125.81
126.03
126.12
129.03
129.05
129.15
129.76
129.90

CH2
CH2
CH2
CH2(2,5)
(CH3)3C
CH2
CH2
CH2
CH2
CH2
CH
CCl4
CH(3,4)
CH(3,4)
CH(3,5)
CH2
CN
CHCH2
CH(2,5)
CHCH2
CH(4,5)
CH2
CH(3,5)
CO2
CH(3,5)
CH(4)
CH(3,5)
C(4)
CH
CH(2,6)
CH(3,5)

allyl acetate
diethyl ether
1,4-dioxane
tetrahydrofuran
tert-butyl alcohol
diallyl carbonate
diglyme
18-crown-6
1,2-dimethoxyethane
diglyme
chloroform
carbon tetrachloride
pyrrole
furan
BHA
propylene
acetonitrile
allyl acetate
pyrrole
diallyl carbonate
imidazole
ethylene
pyridine
carbon dioxide
BHT
toluene
toluene
BHT
benzene
toluene
benzaldehyde

130.23
132.22
133.16
133.76
134.34
135.14
135.89
136.56
137.66
138.19
138.48
140.32
143.49
148.48
150.67
152.51
153.97
155.48
157.04
162.79
167.58
170.61
170.61
170.96
172.31
192.95
193.58
205.87
206.26
208.30
210.36

CH(2,6)
C
CHCH2
CHCH2
CH
CH (4)
CH(2)
CH(4)
C(1)
C(2,6)
C(1)
C(4)
CH(2,5)
C(2,6)
CH(2,6)
C(1)
C(1)
CO
CO
CH
CO2
CO
CO
CO
CO
HCO
CS2
CO
CO
CO
CO

benzaldehyde
hexamethylbenzene
diallyl carbonate
allyl acetate
propylene
benzaldehyde
imidazole
pyridine
benzaldehyde
BHT
toluene
BHA
furan
BHA
pyridine
BHT
BHA
diallyl carbonate
dimethyl carbonate
dimethylformamide
dimethyl malonate
allyl acetate
dimethylacetamide
ethyl acetate
acetic acid
benzaldehyde
carbon disulfide
acetone
(CD3)2CO signal
ethyl methyl ketone
cyclohexanone

S13

Table S17. (CD3)2SO (1H NMR data by chemical shift in ppm)


shift

mult

0.06
0.06
0.20
0.74
0.82
0.820.88
0.86
0.86
0.87
0.91
0.93
1.04
1.06
1.09
1.11
1.15
1.17
1.24
1.25
1.27
1.29
1.36
1.36
1.40
1.55
1.641.66
1.68
1.741.78
1.76
1.91
1.96
1.99
2.03
2.07
2.07
2.09
2.14

proton

s
CH3
s
CH3
s
CH4
m
CH3
s
CH3
m
CH3
t, 7
CH3
t, 7
CH3
t, 7.3
CH3
t, 7
CH2CH3
t, 7
CH3
d, 6
CH3
t, 7
CH3
t, 7
CH3
s
CH3
br s
CH2
t, 7
CH2CH3
br s
CH2
m
CH2
m
CH2
sept, 7.3
CH2
s
ArC(CH3)3
s
ArC(CH3)3
s
CH2
m
CH2(3,4)
m
CH2(4)
dt, 6.4, 1.5
CH3
m
CH2(3,5)
m
CH2(3,4)
s
CH3
s
CH3CO
s
CH3CO
s
CH3
s
CH3
s
CH3CO
s
CH3
s
CH3

impurity

shift

mult

proton

impurity

shift

mult

proton

impurity

silicone grease
hexamethyldisiloxane
methane
pump oil
ethane
H grease8
n-hexane
n-pentane
propane
ethyl methyl ketone
triethylamine
2-propanol
ethanol
diethyl ether
tert-butyl alcohol
pump oil
ethyl acetate
H grease8
n-hexane
n-pentane
propane
BHA
BHT
cyclohexane
pyrrolidine
cyclohexanone
propylene
cyclohexanone
tetrahydrofuran
acetic acid
dimethylacetamide
ethyl acetate
allyl acetate
acetonitrile
ethyl methyl ketone
acetone
hexamethylbenzene

2.18
2.25
2.30
2.43
2.43
2.50
2.53
2.54
2.67
2.73
2.78
2.89
2.94
3.16
3.24
3.24
3.333
3.34
3.38
3.38
3.43
3.44
3.51
3.51
3.53
3.57
3.60
3.65
3.66
3.69
3.78
3.90
4.01
4.03
4.19
4.42
4.52

s
t
s
q, 7
q, 7
p
d, 9.5
s
m
s
s
s
s
s9
s
s
s
s
q, 7
m
s
q, 76
s
m
s
s
m
s
s
s
sept, 6
s
s9
q, 7
s
s
ddd

ArCH3
CH2(2,6)
CH3
CH2CH3
CH2
CHD2
CH3
CH3
CH2(2,5)
CH3
NCH3
CH3
NCH3
CH3
OCH3
CH3
OH
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2(2,5)
CH3
ArOCH3
CH3
CH
CH2
OH
CH2CH3
OH
CH3
CH2

BHT
cyclohexanone
toluene
ethyl methyl ketone
triethylamine
(CD3)2SO residual
HMPA
dimethyl sulfoxide
pyrrolidine
dimethylformamide
dimethylacetamide
dimethylformamide
dimethylacetamide
methanol
diglyme
1,2-dimethoxyethane
water
ethylene glycol
diethyl ether
diglyme
1,2-dimethoxyethane
ethanol
18-crown-6
diglyme
dimethyl malonate
1,4-dioxane
tetrahydrofuran
dimethyl malonate
BHA
dimethyl carbonate
2-propanol
1,2-dichloroethane
methanol
ethyl acetate
tert-butyl alcohol
nitromethane
allyl acetate

4.61
4.61
4.63
4.94
5.03
5.20
5.25
5.29
5.33
5.41
5.76
5.80
5.91
5.93
6.01
6.47
6.52
6.62
6.65
6.73
6.87
7.01
7.18
7.25
7.37
7.39
7.617.67
7.63
7.67
7.697.75
7.79
7.917.93
8.32
8.58
10.02
10.75

ddd
s
s6
dm, 10
dm, 17
ddt
ddt
ddt
ddt
s
s
m
ddt
ddt
m
dd
s
s
s
m
s
s
m
m
s
m
m
s
dd
m
m
m
s
m
s
br t

CH2
H2
OH
CH2(1)
CH2(2)
CHCH2(2)
CHCH2(2)
CHCH2(1)
CHCH2(1)
CH2
CH2
CH
CHCH2
CHCH2
CH(3,4)
CH(3,4)
OH5
ArH
OH5
CH(2,5)
ArH
CH(4,5)
CH(2,4,6)
CH(3,5)
CH
CH(3,5)
CH(3,5)
CH(2)
CH(2,5)
CH(4)
CH(4)
CH(2,6)
CH
CH(2,6)
HCO
NH

diallyl carbonate
hydrogen
ethanol
propylene
propylene
allyl acetate
diallyl carbonate
allyl acetate
diallyl carbonate
ethylene
dichloromethane
propylene
allyl acetate
diallyl carbonate
pyrrole
furan
BHA
BHA
BHT
pyrrole
BHT
imidazole
toluene
toluene
benzene
pyridine
benzaldehyde
imidazole
furan
benzaldehyde
pyridine
benzaldehyde
chloroform
pyridine
benzaldehyde
pyrrole

Table S18. (CD3)2SO (13C{1H} NMR data by chemical shift in ppm)


shift

carbon

4.01
1.03
1.96
6.61
7.61
11.74
13.28
13.88
14.40
15.12
15.67
16.34
16.60
18.51
19.20
20.54
20.68
20.95
20.97
20.99
21.29
21.70
22.05
24.32
25.14
25.26
25.43
26.33
26.46
29.26
29.33
30.30

CH4
CH3
CH3
CH3
CH2CH3
CH3
CH3
CH3
CH3
CH3
CH2
CH3
CH3
CH3
CH3
CH3
CH3CO
CH3
CH3Ar
CH3
CH3
CH2(2,4)
CH2(2,5)
CH2(4)
CH2(3,4)
CH2(3,4)
CH3
CH2
CH2(3,5)
CH3CO
CH2
(CH3)3C

S14

impurity

shift

methane
30.38
acetonitrile
30.56
hexamethyldisiloxane
30.73
ethane
30.95
ethyl methyl ketone
31.25
triethylamine
33.48
n-pentane
34.33
n-hexane
34.42
ethyl acetate
34.76
diethyl ether
35.73
propane
35.83
propane
36.42 (d)
hexamethylbenzene
37.38
ethanol
39.52 (sept)
propylene
40.45
allyl acetate
40.72
ethyl acetate
41.32
acetic acid
45.02
BHT
45.74
toluene
46.51
dimethylacetamide
48.59
n-pentane
52.08
n-hexane
54.63
cyclohexanone
54.84
tetrahydrofuran
54.89
pyrrolidine
56.07
2-propanol
57.98
cyclohexane
58.03
cyclohexanone
59.74
ethyl methyl ketone
62.05
pump oil
62.76
BHA

carbon

impurity

shift

carbon

impurity

shift

carbon

impurity

(CH3)3C
CH3
CH3
CH2(3,4)
(CH3)3C
CH2(3)
(CH3)3C
NCH3
(CH3)3C
CH3
CH2CH3
CH3
NCH3
CD3
CH3
CH2
CH2(2,6)
CH2
CH2
CH2(2,5)
CH3
CH3
CH3
CH2
CH3O
CH2
CH3
CH3
CH2
CH2
CH2

tert-butyl alcohol
acetone
dimethylformamide
n-hexane
BHT
n-pentane
BHT
dimethylacetamide
BHA
dimethylformamide
ethyl methyl ketone
HMPA11
dimethylacetamide
(CD3)2SO signal
dimethyl sulfoxide
dimethyl malonate
cyclohexanone
1,2-dichloroethane
triethylamine
pyrrolidine
methanol
dimethyl malonate
dimethyl carbonate
dichloromethane
BHA
ethanol
diglyme
1,2-dimethoxyethane
ethyl acetate
diethyl ether
ethylene glycol

63.28
64.32
64.92
66.36
66.88
67.03
67.86
69.54
69.85
71.17
71.25
79.16
95.44
107.07
109.62
109.80
116.07
117.32
117.64
117.91
118.32
121.55
123.52
123.84
124.21
124.85
125.29
127.97
128.18
128.30
128.88

CH3
CH2
CH
CH2
(CH3)3C
CH2(2,5)
CH2
CH2
CH2
CH2
CH2
CH
CCl4
CH(3,4)
CH(3,4)
CH(3,5)
CH2
CH(2,5)
CHCH2
CN
CHCH2
CH(4,5)
CH2
CH(3,5)
CO2
CH(3,5)
CH(4)
C(4)
CH(3,5)
CH
CH(2,6)

nitromethane
allyl acetate
2-propanol
1,4-dioxane
tert-butyl alcohol
tetrahydrofuran
diallyl carbonate
diglyme
18-crown-6
1,2-dimethoxyethane
diglyme
chloroform
carbon tetrachloride
pyrrole
furan
BHA
propylene
pyrrole
allyl acetate
acetonitrile
diallyl carbonate
imidazole
ethylene
pyridine
carbon dioxide
BHT
toluene
BHT
toluene
benzene
toluene

129.10
129.45
131.10
132.18
132.71
133.55
134.52
135.15
136.05
136.20
137.35
139.12
141.16
142.82
147.44
149.58
151.47
152.53
154.16
155.76
162.29
166.91
169.54
169.97
170.31
171.93
192.63
193.08
206.31
208.72
210.63

CH(3,5)
CH(2,6)
C
CHCH2
CHCH2
CH
CH (4)
CH(2)
CH(4)
C(1)
C(1)
C(2,6)
C(4)
CH(2,5)
C(2,6)
CH(2,6)
C(1)
C(1)
CO
CO
CH
CO2
CO
CO
CO
CO
CS2
HCO
CO
CO
CO

benzaldehyde
benzaldehyde
hexamethylbenzene
diallyl carbonate
allyl acetate
propylene
benzaldehyde
imidazole
pyridine
benzaldehyde
toluene
BHT
BHA
furan
BHA
pyridine
BHT
BHA
diallyl carbonate
dimethyl carbonate
dimethylformamide
dimethyl malonate
dimethylacetamide
allyl acetate
ethyl acetate
acetic acid
carbon disulfide
benzaldehyde
acetone
ethyl methyl ketone
cyclohexanone

Table S19. CD3CN (1H NMR data by chemical shift in ppm)


shift

mult

0.07
0.08
0.20
0.85
0.85
0.89
0.89
0.90
0.96
0.96
1.09
1.12
1.12
1.16
1.20
1.27
1.28
1.29
1.33
1.39
1.40
1.44
1.61
1.671.72
1.70
1.791.84
1.80
1.94
1.96
1.96
1.97
1.97
2.02
2.06
2.08
2.13
2.16

proton

s
CH3
s
CH3
s
CH4
s
CH3
m
CH3
t, 7
CH3
t, 7
CH3
t, 7.3
CH3
t, 7
CH2CH3
t, 7
CH3
d, 6
CH3
t, 7
CH3
t, 7
CH3
s
CH3
t, 7
CH2CH3
br s
CH2
m
CH2
m
CH2
sept, 7.3
CH2
s
ArC(CH3)3
s
ArC(CH3)3
s
CH2
m
CH2(3,4)
m
CH2(4)
dt, 6.4, 1.5
CH3
m
CH2(3,5)
m
CH2(3,4)
p
CHD2
s
CH3
s
CH3
s
CH3CO
s
CH3CO
s
CH3
s
CH3CO
s
CH3
s
OH
9
s
OH

impurity

shift

mult

proton

impurity

shift

mult

proton

impurity

hexamethyldisiloxane
silicone grease
methane
ethane
pump oil
n-hexane
n-pentane
propane
ethyl methyl ketone
triethylamine
2-propanol
diethyl ether
ethanol
tert-butyl alcohol
ethyl acetate
pump oil
n-hexane
n-pentane
propane
BHT
BHA
cyclohexane
pyrrolidine
cyclohexanone
propylene
cyclohexanone
tetrahydrofuran
CD3CN residual
acetic acid
acetonitrile
dimethylacetamide
ethyl acetate
allyl acetate
ethyl methyl ketone
acetone
water
methanol

2.18
2.19
2.22
2.27
2.33
2.43
2.45
2.47
2.50
2.57
2.697
2.75
2.77
2.83
2.89
2.96
3.28
3.28
3.29
3.38
3.42
3.45
3.45
3.51
3.51
3.53
3.54
3.60
3.64
3.68
3.72
3.72
3.81
3.87
4.06
4.31
4.53

s
s
s
t
s
q, 7
q, 7
s6
s
d, 9.5
m7
m
s
s
s
s
s
s9
s
s
q, 7
m
s
s
m7
m
q, 76
s
m
s
s
s
s
sept, 6
q, 7
s
ddd

OH
CH3
ArCH3
CH2(2,6)
CH3
CH2CH3
CH2
OH
CH3
CH3
OH7
CH2(2,5)
CH3
NCH3
CH3
NCH3
CH3
CH3
OCH3
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2(2,5)
CH3
ArOCH3
CH3
CH2
CH
CH2CH3
CH3
CH2

tert-butyl alcohol
hexamethylbenzene
BHT
cyclohexanone
toluene
ethyl methyl ketone
triethylamine
ethanol
dimethyl sulfoxide
HMPA
ethylene glycol7
pyrrolidine
dimethylformamide
dimethylacetamide
dimethylformamide
dimethylacetamide
1,2-dimethoxyethane
methanol
diglyme
dimethyl malonate
diethyl ether
diglyme
1,2-dimethoxyethane
18-crown-6
ethylene glycol
diglyme
ethanol
1,4-dioxane
tetrahydrofuran
dimethyl malonate
BHA
dimethyl carbonate
1,2-dichloroethane
2-propanol
ethyl acetate
nitromethane
allyl acetate

4.57
4.61
4.93
4.98
5.04
5.20
5.21
5.25
5.29
5.34
5.41
5.44
5.85
5.93
5.96
6.10
6.44
6.73
6.75
6.97
7.01
7.107.30
7.107.30
7.33
7.37
7.52
7.57
7.577.61
7.58
7.677.71
7.73
7.897.91
7.92
8.57
9.27
10.01

s
ddd
dm, 10
s
dm, 17
s
ddt
ddt
ddt
ddt
s
s
m
ddt
ddt
m
dd
s
m
s
s
m
m
m
s
dd
s
m
s
m
m
m
s
m
br t
s

H2
CH2
CH2(1)
OH5
CH2(2)
OH5
CHCH2(2)
CHCH2(2)
CHCH2(1)
CHCH2(1)
CH2
CH2
CH
CHCH2
CHCH2
CH(3,4)
CH(3,4)
ArH
CH(2,5)
ArH
CH(4,5)
CH(2,4,6)
CH(3,5)
CH(3,5)
CH
CH(2,5)
CH(2)
CH(3,5)
CH
CH(4)
CH(4)
CH(2,6)
CH
CH(2,6)
NH
HCO

hydrogen
diallyl carbonate
propylene
BHA
propylene
BHT
allyl acetate
diallyl carbonate
allyl acetate
diallyl carbonate
ethylene
dichloromethane
propylene
allyl acetate
diallyl carbonate
pyrrole
furan
BHA
pyrrole
BHT
imidazole
toluene
toluene
pyridine
benzene
furan
imidazole
benzaldehyde
chloroform
benzaldehyde
pyridine
benzaldehyde
dimethylformamide
pyridine
pyrrole
benzaldehyde

Table S20. CD3CN (13C{1H} NMR data by chemical shift in ppm)


shift

carbon

4.61
1.32 (sept)
1.79
2.07
6.99
8.14
12.38
14.37
14.43
14.54
15.63
16.73
16.91
16.94
18.80
19.48
20.73
21.02
21.16
21.23
21.50
21.76
23.08
23.40
25.55
25.62
26.27
26.34
27.63
27.80
29.60
30.55

CH4
CD3
CH3
CH3
CH3
CH2CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH2
CH3
CH3
CH3
CH3
CH3
CH3CO
CH3Ar
CH3
CH3
CH2(2,4)
CH2(2,5)
CH3
CH2(4)
CH2(3,4)
CH2(3,4)
CH2
CH2(3,5)
CH3CO
(CH3)3C

S15

impurity
methane
CD3CN signal
acetonitrile
hexamethyldisiloxane
ethane
ethyl methyl ketone
triethylamine
n-pentane
n-hexane
ethyl acetate
diethyl ether
propane
propane
hexamethylbenzene
ethanol
propylene
acetic acid
allyl acetate
ethyl acetate
BHT
toluene
dimethylacetamide
n-pentane
n-hexane
2-propanol
cyclohexanone
tetrahydrofuran
pyrrolidine
cyclohexane
cyclohexanone
ethyl methyl ketone
BHA

shift

carbon

impurity

shift

carbon

impurity

shift

carbon

impurity

30.68
30.86
30.91
31.32
31.50
32.36
34.89
35.05
35.17
35.48
36.57
37.09
37.10 (d)
38.26
41.31
41.77
42.44
45.54
47.10
47.57
49.90
52.95
55.32
55.39
55.94
57.96
58.89
58.90
60.98
63.66
64.22
64.30

(CH3)3C
CH2
CH3
CH3
(CH3)3C
CH2(3,4)
CH2(3)
(CH3)3C
NCH3
(CH3)3C
CH3
CH2CH3
CH3
NCH3
CH3
CH2
CH2(2,6)
CH2
CH2
CH2(2,5)
CH3
CH3
CH2
CH3
CH3O
CH2
CH3
CH3
CH2
CH3
CH2
CH

tert-butyl alcohol
pump oil
acetone
dimethylformamide
BHT
n-hexane
n-pentane
BHT
dimethylacetamide
BHA
dimethylformamide
ethyl methyl ketone
HMPA11
dimethylacetamide
dimethyl sulfoxide
dimethyl malonate
cyclohexanone
1,2-dichloroethane
triethylamine
pyrrolidine
methanol
dimethyl malonate
dichloromethane
dimethyl carbonate
BHA
ethanol
1,2-dimethoxyethane
diglyme
ethyl acetate
nitromethane
ethylene glycol
2-propanol

65.55
66.32
67.72
68.33
68.74
69.09
70.99
71.22
72.47
72.63
79.17
96.68
108.31
110.49
111.35
116.12
118.06
118.26
118.26
118.47
118.86
122.78
123.69
125.89
126.28
126.38
127.76
129.23
129.32
129.61
129.94

CH2
CH2
CH2
CH2(2,5)
(CH3)3C
CH2
CH2
CH2
CH2
CH2
CH
CCl4
CH(3,4)
CH(3,4)
CH(3,5)
CH2
CHCH2
CN
CN
CH(2,5)
CHCH2
CH(4,5)
CH2
CO2
CH(4)
CH(3,5)
CH(3,5)
CH(3,5)
CH
C(4)
CH(2,6)

allyl acetate
diethyl ether
1,4-dioxane
tetrahydrofuran
tert-butyl alcohol
diallyl carbonate
diglyme
18-crown-6
1,2-dimethoxyethane
diglyme
chloroform
carbon tetrachloride
pyrrole
furan
BHA
propylene
allyl acetate
CD3CN signal
acetonitrile
pyrrole
diallyl carbonate
imidazole
ethylene
carbon dioxide
toluene
BHT
pyridine
toluene
benzene
BHT
toluene

130.07
130.42
132.61
133.20
133.83
134.78
135.40
136.33
136.89
137.62
138.13
138.90
140.20
143.74
148.39
150.76
152.42
154.02
155.66
157.26
163.31
168.07
171.31
171.32
171.68
173.21
193.60
193.64
207.43
209.88
211.99

CH(3,5)
CH(2,6)
C
CHCH2
CHCH2
CH
CH (4)
CH(2)
CH(4)
C(1)
C(2,6)
C(1)
C(4)
CH(2,5)
C(2,6)
CH(2,6)
C(1)
C(1)
CO
CO
CH
CO2
CO
CO
CO
CO
CS2
HCO
CO
CO
CO

benzaldehyde
benzaldehyde
hexamethylbenzene
diallyl carbonate
allyl acetate
propylene
benzaldehyde
imidazole
pyridine
benzaldehyde
BHT
toluene
BHA
furan
BHA
pyridine
BHT
BHA
diallyl carbonate
dimethyl carbonate
dimethylformamide
dimethyl malonate
dimethylacetamide
allyl acetate
ethyl acetate
acetic acid
carbon disulfide
benzaldehyde
acetone
ethyl methyl ketone
cyclohexanone

Table S21. TFE-d3 (1H NMR data by chemical shift in ppm)


shift

mult

0.08
0.16
0.18
0.85
0.880.94
0.90
0.90
0.91
0.99
1.05
1.20
1.20
1.22
1.26
1.28
1.31
1.31
1.33
1.33
1.33
1.41
1.43
1.44
1.47
1.70
1.751.78
1.871.92
1.91
1.93
1.95
2.03
2.06
2.07
2.09
2.16
2.19

proton

s
CH3
s
CH3
s
CH4
s
CH3
m
CH3
t, 7
CH3
t, 7.3
CH3
t, 7
CH3
m
CH3
t, 7
CH2CH3
t, 7
CH3
d, 6
CH3
t, 7
CH3
t, 7
CH2CH3
s
CH3
m
CH2
t, 7
CH3
br s
CH2
m
CH2
sept, 7.3
CH2
br s
CH2
s
ArC(CH3)3
s
ArC(CH3)3
s
CH2
dt, 6.4, 1.5
CH3
m
CH2(4)
m
CH2(3,5)
m
CH2(3,4)
m
CH2(3,4)
s
CH3
s
CH3CO
s
CH3
s
CH3
s
CH3CO
s
CH3CO
s
CH3

impurity

shift

mult

proton

impurity

shift

mult

proton

impurity

hexamethyldisiloxane
silicone grease
methane
ethane
H grease8
n-pentane
propane
n-hexane
pump oil
ethyl methyl ketone
diethyl ether
2-propanol
ethanol
ethyl acetate
tert-butyl alcohol
n-hexane
triethylamine
H grease8
n-pentane
propane
pump oil
BHT
BHA
cyclohexane
propylene
cyclohexanone
cyclohexanone
tetrahydrofuran
pyrrolidine
acetonitrile
ethyl acetate
acetic acid
allyl acetate
dimethylacetamide
ethyl methyl ketone
acetone

2.20
2.24
2.24
2.33
2.38
2.49
2.63
2.63
2.88
2.94
2.98
3.05
3.11
3.12
3.40
3.41
3.41
3.44
3.58
3.61
3.62
3.64
3.66
3.67
3.71
3.71
3.72
3.76
3.76
3.77
3.78
3.79
3.88
4.05
4.14
4.28

s
s
s
s
t
q, 7
s
d, 9.5
s
s
s
s
m
q, 7
s
s
s
s
q, 7
s
m
s
s
m
s
q, 7
s
s
s
s
m
s
tq
sept, 6
q, 7
s

OH
ArCH3
CH3
CH3
CH2(2,6)
CH2CH3
CH3
CH3
CH3
NCH3
CH3
NCH3
CH2(2,5)
CH2
CH3
OCH3
CH2
CH3
CH2
CH2
CH2
CH2
OH
CH2
CH2
CH2
CH2
CH3
CH2
CH3
CH2(2,5)
ArOCH3
CDH
CH
CH2CH3
CH3

tert-butyl alcohol
BHT
hexamethylbenzene
toluene
cyclohexanone
ethyl methyl ketone
dimethyl sulfoxide
HMPA
dimethylformamide
dimethylacetamide
dimethylformamide
dimethylacetamide
pyrrolidine
triethylamine
1,2-dimethoxyethane
diglyme
dimethyl malonate
methanol
diethyl ether
1,2-dimethoxyethane
diglyme
18-crown-6
water
diglyme
1,2-dichloroethane
ethanol
ethylene glycol
dimethyl malonate
1,4-dioxane
dimethyl carbonate
tetrahydrofuran
BHA
TFE-d3 residual
2-propanol
ethyl acetate
nitromethane

4.53
4.58
4.62
4.93
5.02
5.03
5.24
5.25
5.28
5.32
5.35
5.40
5.87
5.92
5.93
6.24
6.42
6.84
6.87
7.03
7.06
7.107.30
7.107.30
7.33
7.36
7.40
7.44
7.567.59
7.61
7.687.72
7.82
7.86
7.907.92
8.45
9.88

s
ddd
ddd
dm, 10
s
dm, 17
s
ddt
ddt
ddt
ddt
s
m
ddt
ddt
m
dd
m
s
s
s
m
m
s
s
m
dd
m
s
m
m
s
m
m
s

H2
CH2
CH2
CH2(1)
OH
CH2(2)
CH2
CHCH2(2)
CHCH2(2)
CHCH2(1)
CHCH2(1)
CH2
CH
CHCH2
CHCH2
CH(3,4)
CH(3,4)
CH(2,5)
ArH
CH(4,5)
ArH
CH(2,4,6)
CH(3,5)
CH
CH
CH(3,5)
CH(2,5)
CH(3,5)
CH(2)
CH(4)
CH(4)
CH
CH(2,6)
CH(2,6)
HCO

hydrogen
allyl acetate
diallyl carbonate
propylene
TFE-d3 residual
propylene
dichloromethane
allyl acetate
diallyl carbonate
allyl acetate
diallyl carbonate
ethylene
propylene
diallyl carbonate
allyl acetate
pyrrole
furan
pyrrole
BHA
imidazole
BHT
toluene
toluene
chloroform
benzene
pyridine
furan
benzaldehyde
imidazole
benzaldehyde
pyridine
dimethylformamide
benzaldehyde
pyridine
benzaldehyde

Table S22. TFE-d3 (13C{1H} NMR data by chemical shift in ppm)


shift

carbon

impurity

shift

carbon

impurity

shift

carbon

impurity

shift

carbon

impurity

5.88
1.00
2.09
2.87
7.01
8.29
9.51
14.36
14.54
14.63
15.33
16.93
17.04
17.46
18.11
19.63
20.91
21.10
21.18
21.34
21.40
21.62
23.75
24.06
25.21
25.73
26.00
26.69
28.34
28.56
29.64
30.80

CH4
CH3
CH3
CH3
CH3
CH2CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH2
CH3
CH3
CH3
CH3
CH3CO
CH3Ar
CH3
CH3
CH2(2,4)
CH2(2,5)
CH3
CH2(3,4)
CH2(4)
CH2(3,4)
CH2
CH2(3,5)
CH3CO
(CH3)3C

methane
acetonitrile
hexamethyldisiloxane
silicone grease
ethane
ethyl methyl ketone
triethylamine
ethyl acetate
n-pentane
n-hexane
diethyl ether
propane
hexamethylbenzene
propane
ethanol
propylene
acetic acid
allyl acetate
ethyl acetate
BHT
dimethylacetamide
toluene
n-pentane
n-hexane
2-propanol
pyrrolidine
cyclohexanone
tetrahydrofuran
cyclohexane
cyclohexanone
ethyl methyl ketone
BHA

30.96
31.01
31.07
31.85
32.35
33.17
35.69
35.76
36.07
36.28
37.21 (d)
37.76
38.23
39.06
40.06
42.13
43.16
45.28
47.43
48.45
50.67
54.00
54.46
56.17
57.55
59.40
59.52
59.68
61.5 (qp)
62.70
63.17
64.87

CH3
(CH3)3C
(CH3)3C
CH2
CO
CH2(3,4)
(CH3)3C
CH2(3)
(CH3)3C
NCH3
CH3
CH3
CH2CH3
NCH3
CH3
CH2
CH2(2,6)
CH2
CH2(2,5)
CH2
CH3
CH3
CH2
CH3
CH3O
CH3
CH3
CH2
CD2
CH2
CH3
CH2

dimethylformamide
BHT
tert-butyl alcohol
pump oil
acetone
n-hexane
BHT
n-pentane
BHA
dimethylacetamide
HMPAi
dimethylformamide
ethyl methyl ketone
dimethylacetamide
dimethyl sulfoxide
dimethyl malonate
cyclohexanone
1,2-dichloroethane
pyrrolidine
triethylamine
methanol
dimethyl malonate
dichloromethane
dimethyl carbonate
BHA
diglyme
1,2-dimethoxyethane
ethanol
TFE-d3 signal
ethyl acetate
nitromethane
ethylene glycol

66.69
67.55
67.61
68.52
69.53
70.69
70.80
71.33
72.35
72.87
73.05
78.83
97.74
108.85
111.06
112.90
116.38
118.95
119.39
119.61
120.15
122.93
124.08
126.27
126.28 (q)
126.82
126.92
127.11
129.79
129.84
130.58
130.62

CH
CH2
CH2
CH2
CH2(2,5)
CH2
CH2
CH2
(CH3)3C
CH2
CH2
CH
CCl4
CH(3,4)
CH(3,4)
CH(3,5)
CH2
CN
CHCH2
CH(2,5)
CHCH2
CH(4,5)
CH2
CH(3,5)
CF3
CH(4)
CO2
CH(3,5)
CH(3,5)
CH
CH(2,6)
C(4)

2-propanol
diethyl ether
allyl acetate
1,4-dioxane
tetrahydrofuran
diallyl carbonate
18-crown-6
diglyme
tert-butyl alcohol
1,2-dimethoxyethane
diglyme
chloroform
carbon tetrachloride
pyrrole
furan
BHA
propylene
acetonitrile
allyl acetate
pyrrole
diallyl carbonate
imidazole
ethylene
pyridine
TFE-d3 signal
toluene
carbon dioxide
BHT
toluene
benzene
toluene
BHT

130.82
131.78
132.72
133.33
134.04
136.00
136.58
137.17
137.84
138.59
139.62
139.92
140.23
144.22
149.76
150.52
153.46
153.74
157.39
159.04
166.01
170.88
175.55
175.74
175.98
177.96
196.26
197.63
214.98
218.31
221.30

CH(3,5)
CH(2,6)
CHCH2
CHCH2
C
CH
CH(2)
CH (4)
C(1)
C(2,6)
CH(4)
C(1)
C(4)
CH(2,5)
CH(2,6)
C(2,6)
C(1)
C(1)
CO
CO
CH
CO2
CO
CO
CO
CO
CS2
HCO
CH3
CO
CO

benzaldehyde
benzaldehyde
diallyl carbonate
allyl acetate
hexamethylbenzene
propylene
imidazole
benzaldehyde
benzaldehyde
BHT
pyridine
toluene
BHA
furan
pyridine
BHA
BHT
BHA
diallyl carbonate
dimethyl carbonate
dimethylformamide
dimethyl malonate
ethyl acetate
dimethylacetamide
allyl acetate
acetic acid
carbon disulfide
benzaldehyde
acetone
ethyl methyl ketone
cyclohexanone

S16

Table S23. CD3OD (1H NMR data by chemical shift in ppm)


shift

mult

0.07
0.10
0.20
0.85
0.860.91
0.860.93
0.90
0.90
0.91
1.01
1.05
1.15
1.18
1.19
1.24
1.29
1.29
1.29
1.29
1.34
1.40
1.40
1.41
1.45
1.70
1.72
1.741.76
1.851.87
1.87
1.99
2.01
2.03
2.05
2.07
2.12
2.15

proton

s
CH3
s
CH3
s
CH4
s
CH3
m
CH3
m
CH3
t, 7
CH3
t, 7
CH3
t, 7.3
CH3
t, 7
CH2CH3
t, 7
CH3
d, 6
CH3
t, 7
CH3
t, 7
CH3
t, 7
CH2CH3
br s
CH2
m
CH2
m
CH2
br s
CH2
sept, 7.3
CH2
s
CH3
s
ArC(CH3)3
s
ArC(CH3)3
s
CH2
dt, 6.4, 1.5
CH3
m
CH2(3,4)
m
CH2(4)
m
CH2(3,5)
m
CH2(3,4)
s
CH3
s
CH3CO
s
CH3
s
CH3
s
CH3CO
s
CH3CO
s
CH3

impurity

shift

mult

proton

impurity

shift

mult

proton

impurity

hexamethyldisiloxane
silicone grease
methane
ethane
pump oil
H grease8
n-hexane
n-pentane
propane
ethyl methyl ketone
triethylamine
2-propanol
diethyl ether
ethanol
ethyl acetate
H grease8
n-hexane
n-pentane
pump oil
propane
tert-butyl alcohol
BHT
BHA
cyclohexane
propylene
pyrrolidine
cyclohexanone
cyclohexanone
tetrahydrofuran
acetic acid
ethyl acetate
acetonitrile
allyl acetate
dimethylacetamide
ethyl methyl ketone
acetone

2.19
2.21
2.32
2.34
2.50
2.58
2.64
2.65
2.80
2.86
2.92
2.99
3.31
3.31
3.34
3.35
3.35
3.44
3.49
3.52
3.58
3.59
3.60
3.61
3.64
3.66
3.71
3.72
3.72
3.74
3.78
3.92
4.09
4.34
4.56

s
s
s
t
q, 7
q, 7
d, 9.5
s
m
s
s
s
p
s
s
s
s
s
q, 7
s
m
s
q, 7
m
s
s
m
s
s
s
s
sept, 6
q, 7
s
ddd

CH3
ArCH3
CH3
CH2(2,6)
CH2CH3
CH2
CH3
CH3
CH2(2,5)
CH3
NCH3
CH3
CD2H
NCH3
CH3
OCH3
CH3
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2(2,5)
ArOCH3
CH3
CH3
CH2
CH
CH2CH3
CH3
CH2

hexamethylbenzene
BHT
toluene
cyclohexanone
ethyl methyl ketone
triethylamine
HMPA
dimethyl sulfoxide
pyrrolidine
dimethylformamide
dimethylacetamide
dimethylformamide
CD3OD residual
dimethylacetamide
methanol
diglyme
1,2-dimethoxyethane
dimethyl malonate
diethyl ether
1,2-dimethoxyethane
diglyme
ethylene glycol
ethanol
diglyme
18-crown-6
1,4-dioxane
tetrahydrofuran
BHA
dimethyl malonate
dimethyl carbonate
1,2-dichloroethane
2-propanol
ethyl acetate
nitromethane
allyl acetate

4.56
4.61
4.85
4.87
4.91
5.01
5.21
5.25
5.30
5.34
5.39
5.49
5.82
5.94
5.94
6.08
6.40
6.71
6.72
6.92
7.05
7.16
7.16
7.33
7.44
7.49
7.567.60
7.667.70
7.67
7.85
7.90
7.907.93
7.97
8.53
10.00

s
ddd
s
s
dm, 10
dm, 17
ddt
ddt
ddt
ddt
s
s
m
ddt
ddt
m
dd
s
m
s
s
m
m
s
m
dd
m
m
s
m
s
m
s
m
s

H2
CH2
OHd
OH
CH2(1)
CH2(2)
CHCH2(2)
CHCH2(2)
CHCH2(1)
CHCH2(1)
CH2
CH2
CH
CHCH2
CHCH2
CH(3,4)
CH(3,4)
ArH
CH(2,5)
ArH
CH(4,5)
CH(2,4,6)
CH(3,5)
CH
CH(3,5)
CH(2,5)
CH(3,5)
CH(4)
CH(2)
CH(4)
CH
CH(2,6)
CH
CH(2,6)
HCO

hydrogen
diallyl carbonate
BHA
water
propylene
propylene
allyl acetate
diallyl carbonate
allyl acetate
diallyl carbonate
ethylene
dichloromethane
propylene
allyl acetate
diallyl carbonate
pyrrole
furan
BHA
pyrrole
BHT
imidazole
toluene
toluene
benzene
pyridine
furan
benzaldehyde
benzaldehyde
imidazole
pyridine
chloroform
benzaldehyde
dimethylformamide
pyridine
benzaldehyde

Table S24. CD3OD (13C{1H} NMR data by chemical shift in ppm)


shift

carbon

4.90
0.85
1.99
2.10
6.98
8.09
11.09
14.39
14.45
14.49
15.46
16.80
16.90
17.19
18.40
19.50
20.56
20.71
20.88
21.32
21.38
21.50
23.38
23.68
25.27
25.86
26.29
26.48
27.96
28.16
29.39
30.67

CH4
CH3
CH3
CH3
CH3
CH2CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH2
CH3
CH3
CH3
CH3
CH3CO
CH3
CH3Ar
CH3
CH2(2,4)
CH2(2,5)
CH3
CH2(4)
CH2(3,4)
CH2(3,4)
CH2
CH2(3,5)
CH3CO
CH3

S17

impurity

shift

methane
30.82
acetonitrile
30.91
hexamethyldisiloxane
31.15
silicone grease
31.35
ethane
31.61
ethyl methyl ketone
32.73
triethylamine
35.30
n-pentane
35.36
n-hexane
35.50
ethyl acetate
35.83
diethyl ether
36.89
propane
37.00 (d)
hexamethylbenzene
37.34
propane
38.43
ethanol
40.45
propylene
41.60
acetic acid
42.61
allyl acetate
45.11
ethyl acetate
46.96
dimethylacetamide
47.23
BHT
49.00 (sept)
toluene
49.86
n-pentane
52.83
n-hexane
54.78
2-propanol
55.25
cyclohexanone
55.96
pyrrolidine
58.26
tetrahydrofuran
59.06
cyclohexane
59.06
cyclohexanone
61.50
ethyl methyl ketone
63.08
acetone
64.30

carbon

impurity

shift

carbon

impurity

shift

carbon

impurity

(CH3)3C
(CH3)3C
(CH3)3C
CH2
CH3
CH2(3,4)
CH2(3)
(CH3)3C
NCH3
(CH3)3C
CH3
CH3
CH2CH3
NCH3
CH3
CH2
CH2(2,6)
CH2
CH2
CH2(2,5)
CD3
CH3
CH3
CH2
CH3
CH3O
CH2
CH3
CH3
CH2
CH3
CH2

BHA
tert-butyl alcohol
BHT
pump oil
dimethylformamide
n-hexane
n-pentane
BHT
dimethylacetamide
BHA
dimethylformamide
HMPAi
ethyl methyl ketone
dimethylacetamide
dimethyl sulfoxide
dimethyl malonate
cyclohexanone
1,2-dichloroethane
triethylamine
pyrrolidine
CD3OD signal
methanol
dimethyl malonate
dichloromethane
dimethyl carbonate
BHA
ethanol
diglyme
1,2-dimethoxyethane
ethyl acetate
nitromethane
ethylene glycol

64.71
66.14
66.88
68.11
68.83
69.35
69.40
71.33
71.47
72.72
72.92
79.44
97.21
108.11
110.33
111.30
116.04
118.06
118.22
118.28
118.74
122.60
123.46
125.53
126.11
126.29
126.31
129.20
129.34
129.49
129.91

CH
CH2
CH2
CH2
CH2(2,5)
CH2
(CH3)3C
CH2
CH2
CH2
CH2
CH
CCl4
CH(3,4)
CH(3,4)
CH(3,5)
CH2
CN
CHCH2
CH(2,5)
CHCH2
CH(4,5)
CH2
CH(3,5)
CH(3,5)
CH(4)
CO2
CH(3,5)
CH
C(4)
CH(2,6)

2-propanol
allyl acetate
diethyl ether
1,4-dioxane
tetrahydrofuran
diallyl carbonate
tert-butyl alcohol
diglyme
18-crown-6
1,2-dimethoxyethane
diglyme
chloroform
carbon tetrachloride
pyrrole
furan
BHA
propylene
acetonitrile
allyl acetate
pyrrole
diallyl carbonate
imidazole
ethylene
pyridine
BHT
toluene
carbon dioxide
toluene
benzene
BHT
toluene

130.12
130.64
132.53
133.25
133.71
134.61
135.60
136.31
137.96
138.35
138.85
139.09
141.36
143.68
149.04
150.07
152.85
154.34
156.28
157.91
164.73
168.70
172.41
172.89
173.32
175.11
193.82
194.11
209.67
212.16
214.69

CH(3,5)
CH(2,6)
C
CHCH2
CHCH2
CH
CH (4)
CH(2)
C(1)
CH(4)
C(1)
C(2,6)
C(4)
CH(2,5)
C(2,6)
CH(2,6)
C(1)
C(1)
CO
CO
CH
CO2
CO
CO
CO
CO
CS2
HCO
CO
CO
CO

benzaldehyde
benzaldehyde
hexamethylbenzene
diallyl carbonate
allyl acetate
propylene
benzaldehyde
imidazole
benzaldehyde
pyridine
toluene
BHT
BHA
furan
BHA
pyridine
BHT
BHA
diallyl carbonate
dimethyl carbonate
dimethylformamide
dimethyl malonate
allyl acetate
ethyl acetate
dimethylacetamide
acetic acid
carbon disulfide
benzaldehyde
acetone
ethyl methyl ketone
cyclohexanone

Table S25. D2O (1H NMR data by chemical shift in ppm)


shift

mult

proton

impurity

shift

mult

proton

impurity

shift

mult

proton

impurity

0.18
0.28
0.82
0.88
0.99
1.17
1.17
1.17
1.24
1.24
1.26
1.30
1.70
1.701.75
1.851.90
1.87
1.88
2.06
2.07
2.08
2.08
2.13
2.19
2.22
2.40
2.57
2.61

s
s
s
t, 7.3
t, 7
t, 7
t, 7
d, 6
s
t, 7
t, 7
sept, 7.3
dt, 6.4, 1.5
m
m
m
m
s
s
s
s
s
s
s
t
q, 7
d, 9.5

CH4
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH2CH3
CH2CH3
CH2
CH3
CH2(4)
CH2(3,5)
CH2(3,4)
CH2(3,4)
CH3
CH3CO
CH3
CH3CO
CH3
CH3CO
CH3
CH2(2,6)
CH2
CH3

methane
hexamethyldisiloxane
ethane
propane
triethylamine
diethyl ether
ethanol
2-propanol
tert-butyl alcohol
ethyl acetate
ethyl methyl ketone
propane
propylene
cyclohexanone
cyclohexanone
pyrrolidine
tetrahydrofuran
acetonitrile
ethyl acetate
acetic acid
dimethylacetamide
allyl acetate
ethyl methyl ketone
acetone
cyclohexanone
triethylamine
HMPA

2.71
2.85
2.90
3.01
3.06
3.07
3.18
3.34
3.37
3.37
3.56
3.60
3.60
3.61
3.65
3.65
3.67
3.69
3.74
3.75
3.78
3.80
4.02
4.14
4.40
4.62

s
s
s
s
s
m
q, 7
s
s
s
q, 7
s
s
m
q, 7
s
m
s
m
s
s
s
sept, 6
q, 7
s
ddd

CH3
CH3
NCH3
CH3
NCH3
CH2(2,5)
CH2CH3
CH3
OCH3
CH3
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH3
CH2(2,5)
CH2
CH3
CH2
CH
CH2CH3
CH3
CH2

dimethyl sulfoxide
dimethylformamide
dimethylacetamide
dimethylformamide
dimethylacetamide
pyrrolidine
ethyl methyl ketone
methanol
diglyme
1,2-dimethoxyethane
diethyl ether
1,2-dimethoxyethane
dimethyl malonate
diglyme
ethanol
ethylene glycol
diglyme
dimethyl carbonate
tetrahydrofuran
1,4-dioxane
dimethyl malonate
18-crown-6
2-propanol
ethyl acetate
nitromethane
allyl acetate

4.69
4.79
4.95
5.06
5.30
5.32
5.37
5.40
5.44
5.90
5.99
5.99
6.26
6.51
6.93
7.14
7.45
7.57
7.577.66
7.767.80
7.78
7.87
7.92
7.977.99
8.52
9.96

ddd
s
dm, 10
dm, 17
ddt
ddt
ddt
ddt
s
m
ddt
ddt
m
dd
m
s
m
dd
m
m
s
m
s
m
m
s

CH2
HOD
CH2(1)
CH2(2)
CHCH2(2)
CHCH2(2)
CHCH2(1)
CHCH2(1)
CH2
CH
CHCH2
CHCH2
CH(3,4)
CH(3,4)
CH(2,5)
CH(4,5)
CH(3,5)
CH(2,5)
CH(3,5)
CH(4)
CH(2)
CH(4)
CH
CH(2,6)
CH(2,6)
HCO

diallyl carbonate
D2O residual
propylene
propylene
allyl acetate
diallyl carbonate
allyl acetate
diallyl carbonate
ethylene
propylene
allyl acetate
diallyl carbonate
pyrrole
furan
pyrrole
imidazole
pyridine
furan
benzaldehyde
benzaldehyde
imidazole
pyridine
dimethylformamide
benzaldehyde
pyridine
benzaldehyde

Table S26. D2O (13C{1H} NMR data by chemical shift in ppm)


shift

carbon

impurity

shift

carbon

impurity

shift

carbon

impurity

shift

carbon

impurity

1.47
2.31
7.87
9.07
13.92
14.77
17.47
21.00
21.03
21.09
21.15
24.38
24.77
25.67
25.86
27.50
29.49
30.29
30.89
32.03
35.03

CH3
CH3
CH2CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3CO
CH3
CH2(4)
CH2(3,4)
CH2(3,4)
CH2(3,5)
CH3CO
(CH3)3C
CH3
CH3
NCH3

acetonitrile
hexamethyldisiloxane
ethyl methyl ketone
triethylamine
ethyl acetate
diethyl ether
ethanol
allyl acetate
acetic acid
dimethylacetamide
ethyl acetate
2-propanol
cyclohexanone
tetrahydrofuran
pyrrolidine
cyclohexanone
ethyl methyl ketone
tert-butyl alcohol
acetone
dimethylformamide
dimethylacetamide

36.46 (d)
37.27
37.54
38.76
39.39
42.02
42.13
46.83
47.19
49.5012
53.65
55.81
58.05
58.67
58.67
62.32
63.17
63.22
64.88
66.42
66.52

CH3
CH2CH3
CH3
NCH3
CH3
CH2(2,6)
CH2
CH2(2,5)
CH2
CH3
CH3
CH3
CH2
CH3
CH3
CH2
CH2
CH3
CH
CH2
CH2

HMPAi
ethyl methyl ketone
dimethylformamide
dimethylacetamide
dimethyl sulfoxide
cyclohexanone
dimethyl malonate
pyrrolidine
triethylamine
methanol
dimethyl malonate
dimethyl carbonate
ethanol
diglyme
1,2-dimethoxyethane
ethyl acetate
ethylene glycol
nitromethane
2-propanol
diethyl ether
allyl acetate

67.19
68.68
68.81
70.05
70.14
70.36
71.49
71.63
96.73
107.83
110.23
118.75
119.03
119.06
119.68
122.43
125.12
129.48
130.09
132.48

CH2
CH2(2,5)
CH2
CH2
CH2
(CH3)3C
CH2
CH2
CCl4
CH(3,4)
CH(3,4)
CHCH2
CHCH2
CH(2,5)
CN
CH(4,5)
CH(3,5)
CH(3,5)
CH(2,6)
CHCH2

1,4-dioxane
tetrahydrofuran
diallyl carbonate
diglyme
18-crown-6
tert-butyl alcohol
1,2-dimethoxyethane
diglyme
carbon tetrachloride
pyrrole
furan
diallyl carbonate
allyl acetate
pyrrole
acetonitrile
imidazole
pyridine
benzaldehyde
benzaldehyde
allyl acetate

132.76
134.70
136.11
136.65
138.27
143.57
149.18
157.78
163.96
165.53
170.12
174.57
174.78
175.26
177.21
191.67
197.25
215.94
218.43
221.22

CHCH2
CH (4)
C(1)
CH(2)
CH(4)
CH(2,5)
CH(2,6)
CO
CO
CH
CO2
CO
CO
CO
CO
HCO
CS2
CO
CO
CO

diallyl carbonate
benzaldehyde
benzaldehyde
imidazole
pyridine
furan
pyridine
diallyl carbonate
dimethyl carbonate
dimethylformamide
dimethyl malonate
dimethylacetamide
allyl acetate
ethyl acetate
acetic acid
benzaldehyde
carbon disulfide
acetone
ethyl methyl ketone
cyclohexanone

S18

References
(1) Gottlieb, H. E.; Kotlyar, V.; Nudelman, A. J. Org. Chem. 1997, 62, 7512.
(2) Except for the compounds in solutions 810, as well as the gas samples,
hexamethylbenzene, and the corrected values (vide supra), all data for the
solvents CDCl3, C6D6, (CD3)2CO, (CD3)2SO, CD3CN, CD3OD, and D2O were
previously reported in ref 1.
(3) A signal for HDO is also observed in (CD3)2SO (3.30 ppm) and (CD3)2CO (2.81
ppm), often seen as a 1:1:1 triplet (2JH,D = 1 Hz).
(4) Splitting pattern observed as a triplet of a non-first-order ABX pattern.
(5) Not all OH signals were observable.
(6) In some solvents, the coupling interaction between the CH2 and the OH protons may
be observed (J = 5 Hz).
(7) In CD3CN, the OH proton was seen as a multiplet at 2.69 ppm, as well as extra
coupling to the CH2 peak.
(8) Apiezon-brand H grease.
(9) In some solvents, the coupling interaction between the CH3 and the OH protons may
be observed (J = 5.5 Hz).
(10) Pyrrolidine was observed to react with the solvent (CD3)2CO.
(11) Phosphorus coupling was observed (2JPC = 3 Hz).
(12) Internal reference; see Experimental Section in text.

S19