strengths of acids in acetonitriletera.chem.ut.ee/~ivo/ha_ut/pka_values_of_acids_in... · 2021. 3....
TRANSCRIPT
doi.org/10.1002/ejoc.202001649
Strengths of Acids in Acetonitrile
Dedicated to the memory of Prof. Ilmar A. Koppel.
Agnes Kütt, Sofja Tshepelevitsh, Jaan Saame, Märt Lõkov, Ivari Kaljurand, Sigrid Selberg, and Ivo Leito*
Eur. J. Org. Chem. 2021, 1407−1419
HI
4−Cl−C6H4−SO(=NTf)−NH−SO2−C6H4−4−NO2
2,3,5−Tricyanocyclopentadiene
2,4−(NO2)2−C6H3−SO3H
4−Cl−C6H4−SO(=NTf)−NH−SO2−C6H4−4−Cl
4−NO2−C6H4−SO2−NH−Tf
(CN)2C=C(CN)OH
2,4,6−Tf3−Phenol
4−NO2−C6H4−C(=NTf)−NH−Tf
4−Cl−C6H4−SO(=NTf)−NH−Tos
[3,5−(CF3)2−C6H3]−JINGLE
4−Cl−C6H4−SO2−NH−Tf
CH(CN)3
(C6F5−SO2)2NH
4−Cl−C6H4−C(=NTf)−NH−Tf
2,4,6−(SO2F)3−Phenol
4−F−C6H4−C(=NTf)−NH−Tf
HBr
C6H5−SO2−NH−Tf
H−TCNP
C6H5−C(=NTf)−NH−Tf
4−Me−C6H4−C(=NTf)−NH−Tf
Tos−NH−Tf
4−NO2−C6H4−SO2−CH(CN)2
4−MeO−C6H4−C(=NTf)−NH−Tf
C6F5−SO2−NH−SO2−C6H3−3−NO2−4Cl
3−NO2−C6H4−SO2−CH(CN)2
[4−F−C6H4][CF3]−NTPA−[H8]
4−NO2−C6H4−SO3H
[Ph][CF3]−NTPA
[4−MeO−C6H4][CF3]−NTPA
3−NO2−C6H4−SO3H
C6F5−SO2−NH−SO2−C6H4−4−NO2
[Ph][C4F9]−NTPA−[H8]
C6F5−SO2−NH−SO2−C6H4−3−NO2
[Ph][CF3]−NTPA−[H8]
[Ph][C8F17]−NTPA−[H8]
[4−MeO−C6H4][CF3]−NTPA−[H8]
4−Cl−C6H4−SO3H
Me−TCNP
(4−Cl−3−NO2−C6H3−SO2)2NH
C6F5−SO2−NH−SO2−C6H4−4−Cl
H2SO4
C6H5−CHTf2
4−NO2−C6H4−SO2−NH−SO2−C6H3−3−NO2−4−Cl
3−NO2−C6H4−SO2−NH−SO2−C6H3−3−NO2−4−Cl
1−C10H7−SO3H
2,4,6−(SO2OCH2CF3)3−Phenol
2,4,6−(SO2OCH2CF2CF2H)3−Phenol
(4−NO2−C6H4−SO2)2NH
(3−NO2−C6H4−SO2)2NH
Ph−SO3H
TosOH
4−Cl−3−NO2−C6H3−SO2−NH−SO2−C6H4−4−Cl
[2,3,4,5,6−(CF3)5−C6]2NH
2,3,4,5,6−(CF3)5−C6−CH(CN)2
4−NO2−C6H4−SO2−NH−SO2−C6H4−4−Cl
4−NO2−C6H4−CO−NH−Tf
2,4−(NO2)2−C6H3−CH(CN)2
4−Cl−3−NO2−C6H3−SO2−NH−Tos
Me−SO3H
4−NO2−C6H4−SO2−NH−Tos
3−NO2−C6H4−SO2−NH−Tos
2,3,4,5,6−(CF3)5−Thiophenol
4−CF3−C6F4−CH(CN)2
(4−Cl−C6H4−SO2)2NH
4−MeO−C6H4−SO2−NH−SO2−C6H4−4−NO2
HCl
4−Cl−C6H4−CO−NH−Tf
2,3,4,6−(CF3)4−C6H−CH(CN)2
2,3,4,5,6−(CF3)5−Phenol
(2,4,6−(NO2)3−C6H2)2NH
4−F−C6H4−CO−NH−Tf
5−NO2−Barbituric acid
Picric acid
C6H5−CO−NH−Tf
4−Cl−C6H4−SO2−NH−Tos
C6F5−NH−SO2−C8F17
C6F5−NH−SO2−C4F9
4−MeO−C6H4−SO2−NH−SO2−C6H4−4−Cl
(C6H5−SO2)2NH
4−Me−C6H4−CO−NH−Tf
C6F5−NH−Tf
4−MeO−C6H4−CO−NH−Tf
4−NO2−C6H4−CH(CN)2
RS−3,5−(CF3)2−Ph−CXCC−Br4−benzoic acid
Ph−SO2−NH−SO2−Me
Tos2NH
2−C10F7−CH(CN)2
3,5−(CF3)2−Ph−CACC−Br4−benzoic acid
[4−F−C6H4]−BPA
3−CF3−4−NO2−Ph−CACC−Br4−benzoic acid
[Ph]−BPA
4−H−C6F4−CH(CN)2
C6F5−CH(CN)2
[9−Phenanthrene]−BPA
2,3,4,5,6−(CF3)5−C6−CH(CN)COOEt
(4−NC5F4)2CHCN
RR−3,5−(CF3)2−Ph−CXCC−Br4−benzoic acid
[2,4,6−i−Pr3−C6H2]−BPA
4−Me−C6F4−CH(CN)2
[9−Phenanthrene]−BPA−[H8]
2−Cl−4,6−(NO2)2−Phenol
4−NO2−C6H4−SO2−NH−CO−C6H4−3−Cl
3−NO2−C6H4−SO2−NH−CO−C6H4−3−Cl
Saccharin
3−CF3−C6H4−CH(CN)2
4−NC5F4−CH(CN)COOEt
4−NC5F4−OH
4−NO2−C6H4−SO2−NH−CO−C6H4−4−Me
(4−NC5F4)(2−C10F7)CHCN
4−CF3−C6F4−CH(CN)COOEt
(4−CF3−C6F4)2CHCN
4−F−2,6−(NO2)2−Phenol
(4−NC5F4)(C6F5)CHCN
4−CF3−2,3,5,6−F4−Phenol
2,4−(NO2)2−Phenol
2,6−(NO2)2−Phenol
2−Me−4,6−(NO2)2−Phenol
Br4−CX−benzoic acid
(4−NC5F4)2NH
4−Cl−C6F4−CH(CN)COOEt
2−C10F7−CH(CN)COOEt
4−Me−C6H4−CH(CN)2
C6F5−CH(CN)COOEt
2,3,4,5,6−Br5−Phenol
2,3,4,5,6−Cl5−Phenol
4−H−C6F4−CH(CN)COOEt
Br4−CF3−CAC−benzoic acid
4−C6F5−2,3,5,6−F4−Phenol
(4−CF3−C6F4)(C6F5)CHCN
(4−NC5F4)(4−CF3−C6F4)NH
[4−(Ph3B)−2,6−Mes2−Pyridine]H
2−C10F7−OH
9−C6F5−Octafluorofluorene
Br4−CA−benzoic acid
(2−C10F7)2CHCN
2,4,6−(SO2F)3−Aniline
1−C10F7−OH
(4−CN−C6F4)(C6F5)NH
(2−C10F7)(C6F5)CHCN
2,3,4,5,6−F5−Phenol
2,3,5,6−F4−Phenol
(2,4,6−Cl3−C6F2)(C6F5)CHCN
2,3,4,5,6−(CN)5−Toluene
2,4,6−Br3−Phenol
(4−Cl−C6F4)(C6F5)CHCN
(4−NC5F4)(C6F5)NH
(CF3)3COH
4−CF3−C6F4−CH2−Tf
(C6F5)2CHCN
(4−H−C6F4)(C6F5)CHCN
Alizarin
9−CN−Fluorene
(4−CF3−C6H4)(C6F5)NH
Benzoic acid
4−NO2−C6H4−CH2−Tf
(4−Me−C6F4)(C6F5)CHCN
C6F5−SO2−NH2
3−NO2−Indole
Retinoic acid
(4−Me−C6F4)2CHCN
3,5−(CF3)2−C6H3−CH2−Tf
2−NO2−Phenol
C6F5−CH(COOEt)2
Sorbic acid
4−CN−C6H4−CH2−Tf
(4−Cl−C6F4)(C6F5)NH
Acetic acid
9−COOMe−Fluorene
2−NO2−Indole
3,5−(CF3)2−Phenol
2,4,6−(NO2)3−Aniline
Fluoradene
3,5−F2−C6H3−CH2−Tf
(C6F5)2NH
C6F5−NH−C(CF3)3
(4−H−C6F4)(C6F5)NH
3,5−(CF3)2−Ph−C−thiourea
4−CF3−C6H4−CH2−Tf
Octafluorofluorene
3−CN−C6H4−CH2−Tf
4−NO2−C6H4−SO2−NH2
2,3,4,5,6−(CF3)5−Aniline
3−NO2−C6H4−SO2−NH2
1,3−Bis(4−NO2−C6H4)urea
2−CF3−Phenol
(4−Me−C6F4)(C6F5)NH
3−CF3−C6H4−CH2−Tf
(4−Me2N−C6F4)(C6F5)NH
3−CF3−C6H4−SO2−NH2
4−CF3−C6H4−SO2−NH2
3−Cl−C6H4−CH2−Tf
4−CF3−Phenol
3−F−C6H4−CH2−Tf
Triazine 1
4−Cl−C6H4−SO2−NH2
3−CN−Indole
(Ph)(C6F5)CHCN
SBoxCH2
4−F−C6H4−SO2−NH2
4−NO2−Indolocarbazole
(4−NO2−C6H4)2NH
(Ph)(4−NC5F4)NH
C6F5−NH−COMe
3−CF3−Phenol
Triazine 2
Ph−SO2−NH2
(4−NC5F4)(4−Me−C6H4)NH
Box2CH2
4−Me−C6H4−SO2−NH2
(Ph)(4−Me−C6F4)CHCN
4−F−C6H4−CH2−Tf
4−Cl−C6H4−CH2−Tf
1,2,3,4−F4−9−Ph−Fluorene
C6H5−CH2−Tf
(3,5−(CF3)2−C6H3)3COH
Me2Box2CH2
6−NO2−Indole
4−NO2−Indole
1−(4−Cl−C6H4)−3−(3,4−Cl2−C6H3)urea
9−C6F5−Fluorene
5−NO2−Indole
2,3,4,5,6−(CF3)5−Toluene
4−CN−2,3,5,6−F4−Aniline
tBu4Box2CH2
Phenol
Indoxyl acetate
7−NO2−Indole
Triazine 3
Indole
Compound
0.58
1.01
0.88
0.90
1.06
1.15
0.63
0.19
0.82
2.58
−0.03
0.53
0.68
0.58
0.02
0.45
0.90
0.38
0.06
1.16
0.96
0.32
0.39
2.61
1.79
1.05
0.02
0.39
0.73
2.70
0.90
0.92
0.89
1.01
1.49
0.25
0.26
1.57
0.90
0.54
2.21
2.10
0.76
0.96
0.21
0.25
0.21
0.48
1.07
1.88
0.06
0.19
0.80
0.08
0.26
0.59
0.10
1.81
0.81
1.73
2.30
1.21
1.48
0.92
0.82
0.26
1.87
1.15
0.27
0.54
0.05
0.06
0.84
0.41
1.12
1.43
0.15
1.04
0.71
0.40
1.89
0.44
0.87
0.90
1.01
1.71
0.03
0.74
1.02
0.93
0.48
1.59
1.37
0.74
0.87
1.60
0.26
1.10
0.35
1.10
0.62
0.03
1.77
1.16
0.90
1.89
0.87
0.19
1.08
0.72
0.61
1.06
1.35
0.28
1.10
0.87
2.06
0.71
2.11
0.10
1.29
0.10
1.06
1.75
1.15
1.74
1.81
1.82
0.46
1.08
0.13
1.15
−0.01
1.20
1.30
1.30
0.82
0.82
1.12
2.00
1.24
0.93
1.06
0.15
0.79
2.12
0.14
1.02
1.52
0.52
0.88
0.73
1.63
1.46
1.05
0.32
1.28
0.59
1.11
0.37
0.83
0.00
0.01
0.20
0.85
1.08
0.31
1.31
1.14
0.85
0.42
1.39
0.48
1.57
1.92
0.41
1.22
2.56
1.48
1.70
1.37
1.94
1.13
0.92
0.79
0.23
1.91
1.74
0.16
0.36
0.380.26
0.59
0.83
0.53
0.47
0.77
0.64
0.90
1.68
1.13
0.94
1.70
0.95
1.73
1.46
1.25
0.42
0.41
0.05
0.78
1.88
0.81
0.71
0.76
0.74
1.04
1.00
0.64
0.25
1.18
1.83
0.08
0.18
1.27
1.21
1.30
1.23
1.12
0.14
1.78
0.04
1.96
0.85
1.13
1.50
0.97
1.96
1.48
1.03
1.54
1.20
1.53
0.97
0.64
0.04
0.44
0.42
0.58
1.28
0.35
0.68
0.67
0.71
0.04
0.60
0.72
0.75
0.26
0.06
0.43
0.44
0.78
1.19
0.28
0.41
0.75
0.81
0.92
0.27
0.32
0.37
0.98
1.51
1.92
0.12
0.39
0.45
0.89
0.79
1.08
1.38
0.14
0.29
0.36
0.53
0.72
0.79
0.91
0.30
0.05
0.13
0.70
1.15
0.53
0.10
0.20
1.020.69
1.02
1.22
1.09
0.62
0.69
1.27
2.26
0.18
0.35
0.33
0.47
0.64
0.96
0.42
0.59
0.38
0.88
1.20
0.41
0.31
1.20
0.20
0.17
1.25
1.31
1.17
0.78
0.43
0.11
0.88
0.02
1.02
1.84
0.73
1.10
0.60
1.49
0.69
0.04
0.89
0.60 0.60
1.43
0.53
0.94
0.56
0.46
0.600.62
0.30
0.39
0.51
1.31
0.05
0.50
0.52
0.72
0.76
0.53
0.72
−0.01 1.03
0.34
1.35
0.48
1.21
0.24
0.32
0.23
0.70
0.09
0.13
1.74
0.23
0.71
0.29
1.32
0.98
0.13
1.25
0.06
0.19
0.49
0.54
1.72
1.64
0.07
0.15
1.60
1.37
0.57
0.27
0.06
0.65
0.280.12
0.88
0.85
1.21
1.06
0.73
0.41
0.47
0.49
0.63
0.53
0.40
0.20
0.00
0.20
0.93
0.31
0.29
0.60
0.71
0.57
0.38
0.10
0.10
1.49
0.97
0.18
0.10
−0.01
0.10
0.97
0.71
0.03
0.53
0.42
0.16
0.53
0.03
1.02
0.03
0.40
1.05
0.38
0.36
0.04
0.21
0.63
0.61
0.91
0.69
0.77
0.22
1.410.70
0.69
1.00
0.75 0.56
0.22
1.02
1.68
1.26
1.20
0.77
1.89
1.65
0.28
0.37
0.80
0.56
0.07
0.23
0.07
0.25
0.19
1.40
0.54
0.56
0.66
0.65
0.64
0.53
0.51
0.45
0.33
0.17 0.44
0.57
0.6
0.14
0.06
0.91
0.14
0.84
0.53
0.32
0.27
0.30
0.78
0.78
0.18
0.51
0.50
−0.01
0.13
1.45
0.48
0.80
0.27
0.32
0.00
0.01
0.40
0.79
0.20
0.41
1.01
0.88
0.72
0.17
0.45
0.11
1.91
0.22
0.22
1.08
0.47
0.23
0.21
0.21
0.15
0.17
0.65
0.53
0.47
0.39
0.08
0.16
0.09 0.51
0.72
0.2
0.47
0.07
0.80
0.16
0.24
0.31
0.98
0.07
0.10
0.34
0.54
0.84
0.11
0.79
0.21
0.07
0.64
0.14
0.30
0.36
0.32
0.02
0.97
0.11
0.31
0.75
0.6
0.29
0.46
0.46
0.86
0.50
0.62
2.8
3.30
3.65
3.96
4.00
4.04
4.36
4.44
4.63
4.78
4.97
4.98
5.0
5.08
5.20
5.22
5.29
5.4
5.52
5.64
5.68
5.82
5.82
6.01
6.05
6.16
6.16
6.22
6.3
6.33
6.35
6.4
6.60
6.65
6.68
6.68
6.69
6.83
7.0
7.36
7.47
7.55
7.6
7.73
7.82
7.84
7.9
7.94
8.14
8.15
8.16
8.2
8.5
8.75
8.76
8.88
9.17
9.49
9.58
9.68
9.97
10.04
10.07
10.12
10.19
10.20
10.29
10.3
10.35
10.42
10.46
10.54
10.65
10.72
11.00
11.07
11.10
11.19
11.25
11.29
11.35
11.46
11.48
11.60
11.61
11.80
11.89
11.97
12.23
12.40
12.46
12.69
12.73
12.98
13.01
13.32
13.41
13.47
13.55
13.63
13.87
13.97
14.23
14.43
14.55
14.57
14.70
14.89
15.39
15.68
16.01
16.07
16.12
16.17
16.39
16.6
16.65
16.74
16.97
17.19
17.20
17.38
17.48
17.57
17.73
17.81
18.00
18.07
18.1
18.1
18.13
18.25
18.45
18.5
18.87
19.20
19.32
19.66
19.7
19.87
20.07
20.1
20.1
20.13
20.14
20.34
20.36
20.39
20.5
21.02
21.09
21.10
21.23
21.35
21.37
21.5
21.92
21.94
22.27
22.77
22.78
22.80
22.84
22.85
22.88
22.97
23.19
23.22
23.5
23.54
23.64
23.8
23.87
23.92
23.96
23.98
24.03
24.11
24.31
24.44
24.49
24.51
24.57
24.57
24.63
24.71
24.9
24.96
25.08
25.13
25.20
25.24
25.47
25.5
25.62
25.85
25.85
26.01
26.16
26.16
26.16
26.18
26.18
26.36
26.45
26.5
26.58
26.63
26.87
26.89
26.95
26.98
27.00
27.06
27.12
27.19
27.21
27.59
27.79
27.89
27.95
28.14
28.18
28.77
28.78
28.85
29.2
29.97
29.99
30.86
32.57
pKa Directly measured ∆pK a
3.5
2.9
2.9
2.9
3.4
2.9
3.2
2.9
3.8
3.6
4.0
3.8
3.3
4.2
4.2
4.8
3.9
4.5
5.0
5.0
5.0
5.0
5.0
logKAHA
Acid type: CH−acids OH−acids NH−acids SH−acids Hydrogen halides