Professional Documents
Culture Documents
Evans
Substrate
H 3O
H 2S
HBr
HCl
15.7
(32)
-1.7
O
X
7.00
-9.00 (0.9)
-8.0
H2O (DMSO)
(1.8)
(15)
HF
3.17
HOCl
7.5
HClO4
-10
HCN
9.4
(12.9)
HN3
4.72
(7.9)
HSCN
4.00
C6H5
o-O2NC6H4
H2SO3
1.9, 7.21
m-O2NC6H4
4.76 (12.3)
1.68
2.66
2.86
2.86
3.12
1.29
0.65
-0.25
3.77
3.6, 10.3
4.2 (11.1)
MeOH
i-PrOH
15.7 (31.2)
15.54 (27.9)
16.5 (29.3)
t-BuOH
17
c-hex3COH
24
CF3CH2OH
12.5 (23.5)
2.17
2.45
8.35
p-O2NC6H4OH
7.14 (10.8)
p-OMeC6H4OH
10.20 (19.1)
m-ClC6H4
3.83
p-ClC6H4
3.99
Ph
N
O H
Ph
HNO3
HNO2
3.29
H2CrO4
-0.98, 6.50
CH3SO3H
-2.6
(1.6)
CF3SO3H
-14
(0.3)
NH4Cl
9.24
B(OH)3
9.23
R= H
trans-CO2H
4.25
3.02, 4.38
HOOH
11.6
cis-CO2H
1.92, 6.23
N
Ph
4.47
Ph
CH3
-6.2
H
O+
-6.5
Me
H
Me
(17.1)
Me
-3.8
O+
Me
O+ H
H
-2.05
O+
-2.2
OH
11.3 (20.1)
Me
Ph
-1.8
Me
p-OMeC6H4
-7.8
OH
Ph
OH
2.94
2.12, 7.21,
12.32
-1.3
OH
o-ClC6H4
H3PO4
OH
m-O2NC6H4OH
3.44
-3.0, 1.99
-12.4
OH
9.95 (18.0)
p-O2NC6H4
H2SO4
N+
Ph
Ph
C6H5OH
2-napthol
(29.4)
(17.9)
(CF3)2CHOH
Substrate
PROTONATED SPECIES
ALCOHOLS
HOH
OH
X= CH3
CH2NO2
CH2F
CH2Cl
CH2Br
CH2I
CHCl2
CCl3
CF3
H
HO
OH
8.88 (13.7)
(NH)
OH
(18.5)
N+ OH
0.79
Me
O
R
Substrate
CARBOXYLIC ACIDS
INORGANIC ACIDS
H 2O
pKa
Substrate
Chem 206
PEROXIDES
OH
Me
MeOOH
11.5
CH3CO3H
8.2
O
S
OH
-2.6
O
Ph
2.1
OH
*Values <0 for H2O and DMSO, and values >14 for water and >35 for DMSO were extrapolated using various methods.
For a comprehensive compilation of Bordwell pKa data see: http://www.chem.wisc.edu/areas/reich/pkatable/index.htm
Substrate
(DMSO) Substrate
PROTONATED NITROGEN
N+H4
9.2
EtN+H3
10.6
(10.5)
i-Pr2N H2
11.05
Et3N+H
10.75 (9.00)
PhN H3
4.6
(3.6)
PhN+(Me)2H
5.20
(2.50)
0.78
Ph2N H2
+
N+ H
Quinuclidine
Morpholine
11.0
7.38
NO2
+
O 2N
NH3
-9.3
NO2
DABCO
N+
N+ H
(26.5)
+NH
R= H
CH3
Ph
CF3
(23.5)
15.1 (25.5)
(23.3)
(17.2)
(26.9)
(24.8)
NH2 (urea)
OEt
Et
-9.0, 12.0
(--, 7.50)
Proton Sponge
NSO2Ph
8.30
NH
N
H
(21.6)
Ph
NH
(17.9)
PROTONATED HETEROCYCLES
(17.3)
(15.0)
SULFONAMIDE
DBU
MeSO2NH2
(17.5)
PhSO2NH2
(16.1)
CF3SO2NH2
6.3
MeSO2NHPh
(12.9)
GUANIDINIUM,
HYRDAZONES,- IDES, & -INES
Me2N
NMe2
NNH2
N
H
DMAP
+
Me2N
(21.6)
NH
HN
R= H (PPTS)
t-Bu
Me
Cl, H
5.21
4.95
6.75
0.72
H
N
NHNH2
(20.95)
(17.2)
PhNHNHPh
(26.1)
NH
HYDROXAMIC ACID
(23.0)
N
HN
(18.6)
1,2,3 triazole
8.88 (13.7)
(NH)
(17.0) N
N
O
N
-10
Bn
H
*Values <0 for H2O and DMSO, and values >14 for water and >35 for DMSO were extrapolated using various methods.
N
H
OH
NH
(3.4)
(0.90)
(4.46)
HETEROCYCLES
PhSO2NHNH2
Ph
6.95
(18.9)
NH
9.2
NH
O
Ph
NH
Me
Ph
(12) (estimate)
(9.7)
12 (20.5)
O
NH2
R= Me
Ph
Ac2NH
(24.1)
(14.7)
(13.6)
NH2
6.90, 9.95
+NH
AMIDINES
N+H2
O
NH3
NH
2.97, 8.82
(2.97, 8.93)
PhCN H
Me
Me
H
H3N+
(37)
NH
(44)
Me
Me
H 2N
N+H2 8.36
N-Me morpholine
38
(36 THF))
26(THF) (30)
(30.6)
(25.0)
(16.9)
TMP
(9.80)
(7.9)
(41)
Substrate
IMIDES
4.7
HN3
NH3
i-Pr2NH
TMS2NH
PhNH2
Ph2NH
NCNH2
5.96
HON H3
Substrate
AMINES
NH
8.12
H2NN H3
H2O (DMSO)
pKa
4.16
2-napthal-N H3
Chem 206
(13.9)
Substrate
Substrate
HYDROCARBONS
O
53
(Me)2CH2
51
CH2=CH2
50
CH4
48
46
(56)
43
(44)
t-BuO
Me
EtO
O
PhH
43
PhCH3
41
(43)
33.5 (32.2)
Ph3CH
31.5 (30.6)
24
(28.8)
23
PhCCH
XC6H4CH3
X= p-CN
(20.0)
(20.4)
13
MeO
(15.7)
(20.9)
(20.1)
LiO
i-Pr
O i-Pr
t-Bu O
Me
Ph
i-Pr
(26.6)
Ph
Me2N
O
SPh
O
N+Me3
(25.9)
(24.9)
O
CN
(18.2)
(18.0)
Me2N
(17.2)
Me
~36
(25.7)
Me2N
Me
X=
19-20 (27.1)
(28.3)
n
n=
(26.3)
O
Ph
15
Et
O
[30.2 (THF)]
Ph
Et2N
20
Et
(26.5)
(19.8)
(18.7)
(13.3)
(15.1)
(27.7)
(26.1)
H2
(14.2)
OMe
Me2N
Me
X= H
Ph
SPh
COCH3
SO2Ph
(26.9)
Me
Me
11
MeO
(30.8)
p-COPh
Me
N+Me3
AMIDES
p-NO2
Me
(23.6)
Me
O
Ph2CH2
HCCH
Ph
EtO
O
Me
Substrate
KETONES
24.5 (30.3)
t-BuO
O
Substrate
ESTERS
(Me)3CH
CH2=CHCH3
Chem 206
X= H
CH3
Ph
COCH3
COPh
CO2Et
CN
F
OMe
OPh
SPh
SePh
NPh2
N+Me3
NO2
SO2Ph
(24.7)
(24.4)
(17.7)
(12.7)
(13.3)
(22.7)
(10.2)
(21.6)
(22.85)
(21.1)
(16.9)
(18.6)
(20.3)
(14.6)
(7.7)
(11.4)
H
OMe
NMe2
Br
CN
(24.7)
(25.7)
(27.5)
(23.8)
(22.0)
4
5
6
7
8
(25.1)
(25.8)
(26.4)
(27.7)
(27.4)
(28.1)
(29.0)
(25.5)
(32.4)
Me
Me
*Values <0 for H2O and DMSO, and values >14 for water and >35 for DMSO were extrapolated using various methods.
For a comprehensive compilation of Bordwell pKa data see: http://www.chem.wisc.edu/areas/reich/pkatable/index.htm
Substrate
X=
H
CH3
Ph
COPh
CONR2
CO2Et
CN
OPh
N+Me3
SPh
SO2Ph
(31.3)
(32.5)
(21.9)
(10.2)
11
(17.1)
(13.1)
(11.1)
(28.1)
(20.6)
(20.8)
(12.0)
MeSCH2SO2Ph
(23.4)
PhSCHPh2
(26.7)
(PhS)3CH
(22.8)
(PrS)3CH
(31.3)
(28.2)
Ph
(26.7)
Ph
(23.0)
N+
O
Ph
(25.2)
(30.2)
Ph
(30.0)
Ph
(35.1)
(29.0)
(29.0)
Ph
X= H
Ph
SOPh
(33)
(27.2)
(18.2)
Ph
(24.5)
CHPh2
SULFONIUM
Me3S+=O
Ph
S+
(18.2)
(16.3)
CH2Ph
Ph
Ph
CO2Me
CN
RSCH2CN
R= Me
Et
i-Pr
t-Bu
(30.7)
(20.8)
(19.1)
(24.3)
(24.0)
(23.6)
(22.9)
PhSCH=CHCH2SPh
(26.3)
BuSH
10-11 (17.0)
(10.3)
PhSH
7
Ph
O
Ph
O
Ph
O
Ph
X= H
CH3
t-Bu
Ph
CH=CH2
CH=CHPh
CCH
CCPh
COPh
COMe
OPh
N+Me3
CN
NO2
SMe
SPh
SO2Ph
PPh2
O
Ph
(27.6)
(30.7)
Me
(24.5)
CF3
Me
NMe
(33)
(22.3)
CHPh2
O
S
O
Me
N+Me2
(14.4)
CF3
Et
(31.1)
Me
O
(18.8)
Me
O
(21.8)
S
O
i-Pr
O
(26.6)
(20.7)
CH2Cl
CF3
Me
NTs
(29.0)
(31.0)
(31.2)
(23.4)
(22.5)
(20.2)
(22.1)
(17.8)
(11.4)
(12.5)
(27.9)
(19.4)
(12.0)
(7.1)
(23.5)
(20.5)
(12.2)
(20.2)
NTs
O
R
R= Me
i-Pr
O
O
S
Ph
NTs
X=
Me
S
N
X= H
Ph
SPh
(30.1)
(PhS)2CHPh
Ph
Me
Me
(30.5)
S
H
SULFONES
(30.8)
(20.8)
(18.7)
(16.9)
(11.8)
(30.8)
(20.3)
(11.0)
(24.9)
SULFOXIDES
PhSCH2X
X= Ph
CN
COCH3
COPh
NO2
SPh
SO2Ph
SO2CF3
POPh2
HETERO-AROMATICS
Substrate
SULFIDES
NITRILES
NC
Substrate
Chem 206
O
S
(32.8)
Et
(PhSO2)2CH2Me
(14.3)
*Values <0 for H2O and DMSO, and values >14 for water and >35 for DMSO were extrapolated using various methods.
For a comprehensive compilation of Bordwell pKa data see: http://www.chem.wisc.edu/areas/reich/pkatable/index.htm
D. H. Ripin, D. A. Evans
Substrate
Substrate
ETHERS
PHOSPHONIUM
+
CH3OPh
(49)
MeOCH2SO2Ph
(30.7)
PhOCH2SO2Ph
(27.9)
PhOCH2CN
(28.1)
(21.1)
MeO
Ph
NITRO
P H4
MeP+H3
-14
RNO2
2.7
Et3P+H
Ph3P+CH3
Ph3P+i-Pr
Ph3P+CH2COPh
9.1
(22.4)
(21.2)
(6.2)
R= CH3
CH2Me
CHMe2
CH2Ph
CH2Bn
Ph3P+CH2CN
(7.0)
PHOSPONATES &
PHOSPHINE OXIDES
SELENIDES
(18.6)
Ph
PhSeCHPh2
(27.5)
(PhSe)2CH2
(31.3)
PhSeCH2Ph
(31.0)
PhSeCH=CHCH2SePh
(27.2)
O
Ph2P
AMMONIUM
X=
+
Me3N CH2X
(27.6)
CN
CO2Et
(16.4)
SO2Ph
(19.4)
(14.6)
COPh
CO2Et
CONEt2
(11.8)
(7.1)
(7.7)
O 2N
Cl
SiMe3
n=
(18.6)
(26.2)
(28.8)
(26.9)
(17.8)
5
6
(16.0)
(17.9)
(15.8)
SPh
CN
(24.9)
(16.9)
N
Ph
PHOSPHINES
(20.6)
Ph2PCH2PPh2
(29.9)
(24.9)
Ph2PCH2SO2Ph
(20.3)
Ph
IMINES
(20.6)
X= CN
(17.2)
(16.7)
(16.9)
(12.2)
(16.2)
Ph
REFERENCES
DMSO:
(EtO)2P
X=
10
CH2SPh
CH2SO2Ph
CH2COPh
O
PhSe
Substrate
(24.3)
Ph
*Values <0 for H2O and DMSO, and values >14 for water and >35 for DMSO were extrapolated using various methods.
For a comprehensive compilation of Brodwell pKa data see: http://www.chem.wisc.edu/areas/reich/pkatable/index.htm
pKa Table.5 10/27/03 1:04 PM
Chem 206
N
N
N
H
N
H
23.0
19.8
18.6
16.4
26.4
N
H
20.8
N
H
24.0
13.3
11.9
O
O
N
H
15.0
N
H
N
H
13.9
N
H
24.0
N
H
N
H
N
H
N
H
N
H
12.1
N
H
N
H
14.8
11.8
18.0