D.H. Ripin, D.A.

Evans pKa's of Inorganic and Oxo-Acids Chem 206

Substrate pKa H2O (DMSO) Substrate pKa H2O (DMSO) Substrate pKa H2O (DMSO) Substrate pKa H2O (DMSO)
INORGANIC ACIDS CARBOXYLIC ACIDS ALCOHOLS PROTONATED SPECIES
H2O 15.7 (32) O
HOH 15.7 (31.2)
+ O
H3O -1.7 X OH MeOH 15.54 (27.9) -12.4
N+
X= CH3 4.76 (12.3) i-PrOH
H2S 7.00 16.5 (29.3) Ph
+
OH
CH2NO2 1.68 OH
t-BuOH 17 (29.4)
HBr -9.00 (0.9) CH2F 2.66 -7.8
c-hex3COH Ph OH
HCl -8.0 (1.8) CH2Cl 2.86 24 +
OH
CH2Br 2.86 CF3CH2OH 12.5 (23.5) -6.2
HF 3.17 (15) Ph CH3
CH2I 3.12 (CF3)2CHOH (17.9)
HOCl 7.5 CHCl2 1.29 H
C6H5OH 9.95 (18.0)
CCl3 0.65 O+ -6.5
HClO4 -10 m-O2NC6H4OH 8.35 Ph Me
CF3 -0.25 H
HCN 9.4 (12.9) H 3.77 p-O2NC6H4OH 7.14 (10.8)
O+ -3.8
HN3 4.72 (7.9) HO 3.6, 10.3 Me Me
p-OMeC6H4OH 10.20 (19.1)
C6H5 4.2 (11.1) 2-napthol (17.1) O+ H
HSCN 4.00 -2.05
o-O2NC6H4 2.17 H
H2SO3 1.9, 7.21 m-O2NC6H4 2.45 OXIMES & HYDROXAMIC ACIDS O+ -2.2
Me H
p-O2NC6H4 3.44 OH +
H2SO4 -3.0, 1.99 N OH
o-ClC6H4 2.94 11.3 (20.1) S -1.8
H3PO4 2.12, 7.21, Ph Ph Me Me
12.32 m-ClC6H4 3.83 O
HNO3 -1.3 OH 8.88 (13.7)
p-ClC6H4 3.99 Ph N (NH) N+ OH 0.79
3.29 + O H
HNO2 o-(CH3)3N C6H4 1.37
OH
H2CrO4 -0.98, 6.50 p-(CH3)3N+C6H4 3.43 Ph N (18.5)
SULFINIC & SULFONIC ACIDS
p-OMeC6H4 4.47 Me
CH3SO3H -2.6 (1.6)
O O O
PEROXIDES
CF3SO3H -14 (0.3) S -2.6
R OH Me OH
NH4Cl 9.24 O
R= H 4.25 MeOOH 11.5
B(OH)3 9.23 S 2.1
trans-CO2H 3.02, 4.38 CH3CO3H 8.2 Ph OH
HOOH 11.6 cis-CO2H 1.92, 6.23

*Values <0 for H2O and DMSO, and values >14 for water and >35 for DMSO were extrapolated using various methods.
D.H. Ripin, D.A. Evans pKa's of Nitrogen Acids Chem 206

Substrate pKa H2O (DMSO) Substrate pKa H2O (DMSO) Substrate pKa H2O (DMSO) Substrate pKa H2O (DMSO)

PROTONATED NITROGEN AMINES IMIDES AMIDINES

N+H4 9.2 (10.5) HN3 4.7 (7.9) O O
NSO2Ph
NH3 38 (41)
EtN+H3 10.6 R NH2
i-Pr2NH (36 THF)) NH 8.30 NH (14.7) (17.3)
+ 11.05 R= Me
i-Pr2N H2 TMS2NH 26(THF) (30) Ph (15.0)
Et3N+H 10.75 (9.00) PhNH2 (30.6) O O

PhN H3+ 4.6 (3.6) Ac2NH (17.9) PROTONATED HETEROCYCLES

Ph2NH (25.0)
PhN+(Me)2H 5.20 (2.50) NCNH2 (16.9) N
(12) (estimate)
+ SULFONAMIDE DBU +
Ph2N H2 0.78 NH (44) N
Me H
+ 4.16 Me
2-napthal-N H3 MeSO2NH2 (17.5) DMAP
+ 8.12 (37) +
H2NN H3 TMP NH PhSO2NH2 (16.1) + NH
Me2N NH 9.2 6.95
+ HN
HON H3 5.96 Me CF3SO2NH2 6.3 (9.7)
Me
Quinuclidine N+ H 11.0 (9.80) H2N N (26.5) R
MeSO2NHPh (12.9)
+
NH
AMIDES & CARBAMATES GUANIDINIUM,
Morpholine O N+H2 8.36 HYRDAZONES,- IDES, & -INES R
O
N+H2 R= H (PPTS) 5.21 (3.4)
N-Me morpholine 7.38 (13.6) (0.90)
NO2 R NH2 t-Bu 4.95
Me2N NMe2
R= H (23.5) Me 6.75 (4.46)
+ NNH2 Cl, H 0.72
O2N NH3 -9.3 CH3 15.1 (25.5) (21.6)
Ph (23.3) Ph Me HETEROCYCLES
NO2 CF3 (17.2) O
H
(18.9) N
N+ H 2.97, 8.82 NH2 (urea) (26.9) Ph NHNH2
DABCO N+ (2.97, 8.93) (20.95)
OEt (24.8)
H O
PhSO2NHNH2 (17.2)
H3N+ +
NH3 6.90, 9.95 Ph (21.6) PhNHNHPh (26.1)
+NH +NH Et N NH (23.0) N (18.6)
3 3 H HN
-9.0, 12.0 O O HYDROXAMIC ACID
Proton Sponge (--, 7.50) (24.1) 12 (20.5) 1,2,3 triazole
NH O NH O
OH 8.88 (13.7)
(17.0) N NH (13.9)
PhCN H + -10 Ph N N O (NH) N
Bn H H
*Values <0 for H2O and DMSO, and values >14 for water and >35 for DMSO were extrapolated using various methods.
D.H. Ripin, D.A. Evans pKa's of CH bonds in Hydrocarbons and Carbonyl Compounds Chem 206

Substrate pKa H2O (DMSO) Substrate pKa H2O (DMSO) Substrate pKa H2O (DMSO) Substrate pKa H2O (DMSO)
O
HYDROCARBONS ESTERS KETONES
(Me)3CH O O Me
53 24.5 (30.3)
X
(Me)2CH2 51 t-BuO Me Me X
O (26.5)
X= H
CH2=CH2 50 Ph (23.6) Ph (19.8) X= H (24.7)
t-BuO (18.7) (25.7)
O SPh OMe
CH4 48 (56) NMe2 (27.5)
(20.0) COCH3 9 (13.3)
N+Me3 (23.8)
46 EtO SO2Ph (15.1) Br
O O O CN (22.0)
CH2=CHCH3 43 (44) 11 (14.2) 19-20 (27.1) O
EtO Me Et Et
O
PhH 43 O O
13 (28.3) n
(15.7)
PhCH3 (43) i-Pr O i-Pr
41 MeO OMe
O (27.7)
Ph2CH2 33.5 (32.2) t-Bu O Me
n= 4 (25.1)
S (20.9) (25.8)
MeO (26.3) 5
Ph3CH 31.5 (30.6)
S Ph i-Pr 6 (26.4)
HCCH 24 O O 7 (27.7)
Ph
[30.2 (THF)] 8 (27.4)
PhCCH 23 (28.8) X
LiO Ph
X= H (24.7)
XC6H4CH3 AMIDES CH3 (24.4) (28.1)
X= p-CN (30.8) (17.7) O
O
(26.6) Ph
p-NO2 (20.4) Ph COCH3 (12.7)
Me2N
O COPh (13.3) (29.0)
p-COPh (26.9) (25.9) O
SPh CO2Et (22.7)
Me Me Me2N
O CN (10.2)
(26.1) (24.9) (21.6) O
N+Me3 F (25.5)
Me Me Et2N OMe (22.85)
O
OPh (21.1)
CN
20 (20.1) N (17.2) SPh (16.9)
SePh (18.6) O
O O (32.4)
(18.2) NPh2 (20.3)
15 (18.0)
Me2N Me N+Me3 (14.6) Me Me
S
H2 ~36 NO2 (7.7)
(25.7)
Me2N Me SO2Ph (11.4)

*Values <0 for H2O and DMSO, and values >14 for water and >35 for DMSO were extrapolated using various methods.
D.H. Ripin, D.A. Evans pKa's of CH bonds at Nitrile, Heteroaromatic, and Sulfur Substituted Carbon Chem 206

Substrate pKa H2O (DMSO) Substrate pKa H2O (DMSO) Substrate pKa H2O (DMSO) Substrate pKa H2O (DMSO)
NITRILES SULFIDES SULFOXIDES SULFONES
O O O
NC X PhSCH2X
S X S X
X= Ph (30.8) Me Ph
X= H (31.3) CN (20.8) X= H (35.1) (29.0)
Ph (29.0) X= H
CH3 (32.5) COCH3 (18.7) SPh (29.0) CH3 (31.0)
Ph (21.9) COPh (16.9) O t-Bu (31.2)
NO2 (11.8) Ph (23.4)
COPh (10.2) S X
SPh (30.8) Ph CH=CH2 (22.5)
CONR2 (17.1) SO2Ph (20.3) X= H (33) CH=CHPh (20.2)
CO2Et (13.1) Ph (27.2) (22.1)
SO2CF3 (11.0) (18.2) CCH
(11.1) POPh2 (24.9) SOPh CCPh (17.8)
CN 11 O
(28.1) (24.5) COPh (11.4)
OPh MeSCH2SO2Ph (23.4) S (12.5)
Ph CHPh2 COMe
N+Me3 (20.6) PhSCHPh2 (26.7) OPh (27.9)
SPh (20.8) SULFONIUM N+Me3 (19.4)
(PhS)3CH (22.8) (12.0)
SO2Ph (12.0) CN
(PrS)3CH (31.3) Me3S+=O (18.2) NO2 (7.1)
Me SMe (23.5)
Me (16.3) (20.5)
HETERO-AROMATICS S SPh
S+
(30.5) Ph CH2Ph SO2Ph (12.2)
S S PPh2 (20.2)
(28.2) H
Ph SULFIMIDES & SULFOXIMINES O O
N (PhS)2CHPh (23.0) S (22.3)
NTs Ph CHPh2
S
(30.1) X S O O
N Ph Ph R (31.1)
S
S R= Me (27.6) Me Me
N X= Ph (30.7) i-Pr (30.7) O O
(26.7) O NTs (18.8)
Ph CO2Me (20.8) S
S (24.5) CF3 Me
CN (19.1) Ph Me O O
RSCH2CN O NMe S (21.8)
Ph (24.3) (33) CF3 i-Pr
N+
(25.2) R= Me S
O O
Ph Me
- Et (24.0) O N+Me2 S (26.6)
O
(23.6) (14.4) CF3
i-Pr S
Ph (30.2) (22.9) Ph Me O O
O
t-Bu O NTs (32.8)
S
PhSCH=CHCH2SPh (26.3) S (20.7) Et Et
Ph (30.0) Ph CH2Cl
S BuSH 10-11 (17.0) (PhSO2)2CH2Me (14.3)
PhSH 7 (10.3)

*Values <0 for H2O and DMSO, and values >14 for water and >35 for DMSO were extrapolated using various methods.
D. H. Ripin, D. A. Evans pKa's of CH bonds at Heteroatom Substituted Carbon & References Chem 206

Substrate pKa H2O (DMSO) Substrate pKa H2O (DMSO) Substrate pKa H2O (DMSO)
REFERENCES
ETHERS PHOSPHONIUM NITRO

P+H4 -14 RNO2 DMSO:

CH3OPh (49)
MeP+H3 2.7 R= CH3 10 (17.2) JACS 97, 7007 (1975)
MeOCH2SO2Ph (30.7) +
Et3P H 9.1 CH2Me (16.7) JACS 97, 7160 (1975)
PhOCH2SO2Ph (27.9) JACS 97, 442 (1975)
Ph3P+CH3 (22.4) CHMe2 (16.9) JACS 105, 6188 (1983)
PhOCH2CN (28.1) Ph3P+i-Pr (21.2) CH2Ph (12.2) JOC 41, 1883 (1976)
O JOC 41, 1885 (1976)
Ph3P+CH2COPh (6.2) CH2Bn (16.2)
MeO (21.1) JOC 41, 2786 (1976)
Ph Ph3P+CH2CN (7.0) CH2SPh (11.8) JOC 41, 2508 (1976)
CH2SO2Ph (7.1) JOC 42, 1817 (1977)
CH2COPh (7.7) JOC 42, 321 (1977)
SELENIDES PHOSPONATES & JOC 42, 326 (1977)
PHOSPHINE OXIDES O2N JOC 43, 3113 (1978)
O O JOC 43, 3095 (1978)
n JOC 43, 1764 (1978)
PhSe (18.6) (EtO)2P X
Ph JOC 45, 3325 (1980)
X= Ph (27.6) (26.9) JOC 45, 3305 (1980)
PhSeCHPh2 (27.5) n= 3 JOC 45, 3884 (1980)
CN (16.4)
(PhSe)2CH2 (31.3) 4 (17.8) JOC 46, 4327 (1981)
CO2Et (18.6) JOC 46, 632 (1981)
5 (16.0)
PhSeCH2Ph (31.0) Cl (26.2) JOC 47, 3224 (1982)
6 (17.9) JOC 47, 2504 (1982)
PhSeCH=CHCH2SePh (27.2) SiMe3 (28.8) (15.8) Acc. Chem. Res. 21, 456 (1988)
O 7
Unpublished results of F. Bordwell
Ph2P X
AMMONIUM IMINES Water:
X= SPh (24.9)
N Ph Advanced Org. Chem., 3rd Ed.
Me3N+CH2X CN (16.9)
(24.3) J. March (1985)
X= CN (20.6) Ph Ph Unpublished results of W. P. Jencks
SO2Ph (19.4) PHOSPHINES Oxime ethers are ~ 10 pka units less
(14.6) acidic than their ketone counterparts THF:
COPh
Streitwieser, JOC 1991, 56, 1989
CO2Et (20.6) Ph2PCH2PPh2 (29.9) JACS 110, 5705 (1988)
CONEt2 (24.9) Ph2PCH2SO2Ph (20.3)

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