pKa's of Inorganic and Oxo-Acids

Substrate

pKa H2O (DMSO)

INORGANIC ACIDS
(32)

15.7

H3O+

-1.7

H2S

7.00

HBr

-9.00 (0.9)

HCl

-8.0
3.17

HOCl

7.5

H2O (DMSO)

O
X

(1.8)
(15)

HClO4

-10

HCN

9.4

(12.9)

HN3

4.72

(7.9)

OH

X= CH3
CH2NO2
CH2F
CH2Cl
CH2Br
CH2I
CHCl2
CCl3
CF3
H
HO
C6H5
o-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)
2.17

HSCN

4.00

H2SO3

1.9, 7.21

m-O2NC6H4

2.45

H2SO4

-3.0, 1.99

p-O2NC6H4

3.44

o-ClC6H4

2.94

m-ClC6H4

3.83

p-ClC6H4

3.99

HNO3

2.12, 7.21,
12.32
-1.3

HNO2

3.29

H2CrO4

-0.98, 6.50

o-(CH3)3N+C6H4 1.37
p-(CH3)3N+C6H4 3.43

CH3SO3H

-2.6

(1.6)

p-OMeC6H4

CF3SO3H

-14

(0.3)

NH4Cl

9.24

B(OH)3
HOOH

H3PO4

Substrate

CARBOXYLIC ACIDS

H2O

HF

pKa

Substrate

4.47

pKa H2O (DMSO)

ALCOHOLS

Substrate

15.7

(31.2)

MeOH
i-PrOH

15.5

Ph

16.5

(27.9)
(29.3)

t-BuOH

17.0

(29.4)

Ph

c-hex3COH

24.0

CF3CH2OH

12.5

(23.5)

9.3

(18.2)

9.95

(18.0)

(CF3)2CHOH
C6H5OH

8.4

p-O2NC6H4OH

7.1
10.2

2-napthol

Ph

OH

-7.8
OH

Ph

CH3

Ph

O+

Ph

(10.8)
(19.1)

Me

11.6

cis-CO2H

1.92, 6.23

Me

O+ H
H

-2.05

O+

-2.2

OH

OH

11.3 (20.1)

-1.8

Me

Me

Ph
OH

N
O H

OH

N+ OH

8.88 (13.7)
(NH)
(18.5)

0.79

(+1.63)

Me
N

Me

OH

(+5.55)

Me

Me

SULFINIC & SULFONIC ACIDS

O

9.23

-3.8

O+

Me

OH

4.25
3.02, 4.38

-6.5
Me

(17.1)

PEROXIDES

R= H
trans-CO2H

-6.2

O
Ph

-12.4
OH

OH

OXIMES & HYDROXAMIC ACIDS

N

N+

m-O2NC6H4OH
p-OMeC6H4OH

pKa H2O (DMSO)

PROTONATED SPECIES

HOH

O
R

Chem 206

MeOOH

11.5

CH3CO3H

8.2

Me

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

pKa Table.1 11/4/05 1:43 PM

D.H. Ripin, D.A. Evans

pKa H2O

Substrate

(DMSO) Substrate

pKa

PROTONATED NITROGEN
N+H4

9.2

EtN+H

10.6

i-Pr2N+H2
Et3N+H
PhN+H3
PhN+(Me)

(10.5)

11.05
10.75 (9.00)

2H

4.6

(3.6)

5.20

(2.50)

Ph2N+H2

0.78

2-napthal-N+H3

4.16

H2NN+H3

8.12

HON+H3

H2O (DMSO)

Quinuclidine

11.0

Me
Me

H2N

(26.5)

AMIDES & CARBAMATES

(9.80)

R= H
(23.5)
CH3 15.1 (25.5)
NH2
Ph
(23.3)
CF3
(17.2)
(urea) NH2
(26.9)
OEt
(24.8)

N+H2 8.36

N-Me morpholine

7.38

NO2
+

O2N

NH3

-9.3

NO2

Et

N+ H

DABCO

2.97, 8.82
(2.97, 8.93)

N+

N
H

6.90, 9.95

+NH
3

+NH

Proton Sponge
PhCN+H

+NH

-9.0, 12.0
(--, 7.50)

(21.6)

Ac2NH

8.30

NH

( )n
O

(20.8)
O

NH

Ph

(17.9)

N
H
NSO2Ph
NH2

H
N

H
N

GUANIDINIUM,
HYRDAZONES,- IDES, & -INES
N+H2
Me2N

(13.6)

NMe2
O

Ph

NNH2
Ph

DBU

(26.1)

(12) (estimate)

N
H
+

N
H

N
H

9.2

NH
HN

R= H (PPTS)
t-Bu
Me
Cl, H

6.95

(19.8)

(13.9)
X= O (24.4)
X= S (27.0)

S
H

(29.4)
Me

NMe
5.21 (3.4)
(0.90)
H
4.95
O
NH
NH
N
(12.1)
N + (18.4)
(4.46)
6.75
H
Me
R
-10
0.72
*Values <0 for H2O and DMSO, and values >14 for water and >35 for DMSO were extrapolated using various methods.

(15)

NH

NH

(18.6)

DMAP
Me2N

N
HN

N
+

(23.0)

NH

X= O (14.8)
X= S (11.8)

(17.2)

PROTONATED HETEROCYCLES

(16.4)

(11.9)

X= O (24)
X X= S (13.3)

N
H
X

PhSO2NHNH2
PhNHNHPh

H
N

Me

(18.9)

(20.95)

(21.6)

NHNH2

(17.3)
(15.0)

R= Me
Ph

HETEROCYCLES

(17.5)
R = Me
Ph
(16.1)
CF3 6.3 (9.7)
MeSO2NHPh
(12.9)
RSO2NH2

n= 1 (24.1)
n= 2 (26.4)

(14.7)

8.88 (13.7)
(NH)

OH

SULFONAMIDE

Bn

NH

NH

H
H3N+

12 (20.5)

Ph

O
NH

pKa H2O (DMSO)

Substrate

HYDROXAMIC ACID & AMIDINES

IMIDES

HN3
4.7 (7.9)
NH3
(41)
38
i-Pr2NH
(36 THF))
26(THF) (30)
TMS2NH
PhNH2 (30.6)
Me
Ph2NH (25.0)
Me
NCNH2 (16.9)
NH (37)
NH (44)

Morpholine

pKa H2O (DMSO)

Substrate

AMINES

5.96
H

N+

Chem 206

pKa's of Nitrogen Acids

N+
Me
Me

(16.5)
i-Pr

N
H

Me

For a comprehensive compilation of Bordwell pKa data see: http://www.chem.wisc.edu/areas/reich/pkatable/index.htm

pKa Table.2 11/4/05 1:43 PM

N+

i-Pr

(24)

D.H. Ripin, D.A. Evans

pKa H2O (DMSO)

Substrate

pKa H2O (DMSO)

Substrate

HYDROCARBONS
O

53

(Me)2CH2

51

CH2=CH2

50

CH4

48
46

(56)

43

(44)

t-BuO

Me

PhH

41

Ph2CH2

33.5 (32.2)

(43)

31.5 (30.6)
24
(28.8)
23

PhCCH
XC6H4CH3
X= p-CN

(30.8)

p-NO2

(20.4)

13

MeO

(15.7)

(20.1)

H2

Et
O

i-Pr

O i-Pr

(20.9)

(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

X=

19-20 (27.1)

(28.3)

Me

n=

i-Pr
O

Ph

(26.3)

[30.2 (THF)]

Ph

LiO

t-Bu O
Ph

15

Et

(26.5)
(19.8)
(18.7)
(13.3)
(12.5)

(27.7)

Et2N

20

X= H
Ph
SPh
COCH3
SO2Ph

Me2N

Me

(14.2)

OMe

(26.9)
Me

Me

11

MeO

(26.1)
Me

(20.0)

AMIDES

p-COPh
Me

N+Me3

Me
O

PhCH3

HCCH

(23.6)

EtO

43

Ph3CH

Ph

O
Me

O
EtO

pKa H2O (DMSO)

Substrate

KETONES

24.5 (30.3)

t-BuO

pKa H2O (DMSO)

Substrate

ESTERS

(Me)3CH

CH2=CHCH3

Chem 206

pKa's of CH bonds in Hydrocarbons and Carbonyl Compounds

X= H
CH3
Ph
COCH3
COPh
CN
F
OMe
OPh
SPh
SePh
NPh2
N+Me3
NO2
SO2Ph

(24.7)
(24.4)
(17.7)
(14.2)
(13.3)
(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

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

pKa Table.3 11/4/05 1:44 PM

pKa's of CH bonds at Nitrile, Heteroaromatic, and Sulfur Substituted Carbon

D.H. Ripin, D.A. Evans

pKa H2O (DMSO)

Substrate

NITRILES
NC

X=

(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+

Ph

(25.2)

O-

(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

SULFIMIDES & SULFOXIMINES

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

(22.3)
CHPh2
O

(27.6)
(30.7)

Me

(24.5)

CF3
O

(33)

CF3
O

Me
NMe
Me
N+Me2

(14.4)

Me
NTs

CH2Cl

CF3

Et

(31.1)
Me
O

(18.8)
Me
O

(21.8)

i-Pr
O

(26.6)

(20.7)

O
S

(32.8)
Et

(PhSO2)2CH2Me

*Values <0 for H2O and DMSO, and values >14 for water and >35 for DMSO were extrapolated using various methods.

pKa Table.4 11/4/05 1:44 PM

(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)
(20.5)
(11.0)
(24.9)

Substrate pKa H2O (DMSO)

SULFOXIDES

PhSCH2X
X= Ph
CN
COCH3
COPh
NO2
SPh
SO2Ph
SO2CF3
POPh2

HETERO-AROMATICS

pKa H2O (DMSO)

Substrate

SULFIDES

H
CH3
Ph
COPh
CONR2
CO2Et
CN
OPh
N+Me3
SPh
SO2Ph

pKa H2O (DMSO)

Substrate

Chem 206

(14.3)

D. H. Ripin, D. A. Evans

pKa's of CH bonds at Heteroatom Substituted Carbon & References

pKa H2O (DMSO)

Substrate

ETHERS
CH3OPh
MeOCH2SO2Ph

(30.7)

PhOCH2SO2Ph

(27.9)

PhOCH2CN

(28.1)

(22.85)
Ph

NITRO

P+H4

-14

RNO2

MeP+H3

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)

X=

O
Ph2P

AMMONIUM

X=
Me3N+CH2X
X= CN
SO2Ph
COPh
CO2Et
CONEt2

(20.0)
(24.9)

(17.2)
(16.7)
(16.9)
(12.2)
(16.2)
(11.8)
(7.1)
(7.7)

O2N

Ph

(27.6)

CN
CO2Et

(16.4)

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
Ph2PCH2PPh2

(29.9)

Ph2PCH2SO2Ph

(20.2)

Ph

JACS 97, 7007 (1975)

JACS 97, 7160 (1975)
JACS 97, 442 (1975)
JACS 105, 6188 (1983)
JOC 41, 1883 (1976)
JOC 41, 1885 (1976)
JOC 41, 2786 (1976)
JOC 41, 2508 (1976)
JOC 42, 1817 (1977)
JOC 42, 321 (1977)
JOC 42, 326 (1977)
JOC 43, 3113 (1978)
JOC 43, 3095 (1978)
JOC 43, 1764 (1978)
JOC 45, 3325 (1980)
JOC 45, 3305 (1980)
JOC 45, 3884 (1980)
JOC 46, 4327 (1981)
JOC 46, 632 (1981)
JOC 47, 3224 (1982)
JOC 47, 2504 (1982)
Acc. Chem. Res. 21, 456 (1988)
Unpublished results of F. Bordwell
Water:

IMINES

(20.6)
(19.4)
(14.6)

10

(EtO)2P

REFERENCES
DMSO:

CH2SPh
CH2SO2Ph
CH2COPh

O
PhSe

pKa H2O (DMSO)

Substrate

PHOSPHONIUM
(49)

MeO

pKa H2O (DMSO)

Substrate

Chem 206

(24.3)

Ph

Oxime ethers are ~ 10 pka units less

acidic than their ketone counterparts
Streitwieser, JOC 1991, 56, 1989

Advanced Org. Chem., 3rd Ed.

J. March (1985)
Unpublished results of W. P. Jencks
THF:
JACS 110, 5705 (1988)
See cited website below for additional
data

*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 11/4/05 1:45 PM

DMSO Acidities of Common Heterocycles

Bordwell, ACR, 1988, 21, 456
Bordwell http://www.chem.wisc.edu/areas/reich/pkatable/index.htm
N

N
N
N
H

N
H

23.0

19.8

18.6

16.4

N
H

20.8

24.0

N
H

13.9

11.9

18.0

O
O

N
H

N
H

N
H

O
O

N
H

N
H

N
H

N
H

15.0

12.1

N
H

26.4

24.0
Me

S
S

H
N
H

S
N
H

N
H

Me

S
Me

N+
Me

Me

H
N+

H
Me

N+

Me
Me

13.3

Pka Table.6.cdx 11/4/05 1:45 PM

14.8

11.8

29.4

16.5

18.4

Me

24

Me