O Et N H Ph
(21.6)
Ph O Me
R= H (PPTS) t-Bu Me Cl, H
5.21 4.95 6.75 0.72
(3.4) (0.90) (4.46)
HETEROCYCLES (18.9)
H N
DABCO
H H3N+
N+ H N+
2.97, 8.82 (2.97, 8.93) 6.90, 9.95
-2.6
OH
R= H trans-CO2H cis-CO2H
MeOOH CH3CO3H
2.1
OH
*Values <0 for H2O and DMSO, and values >14 for water and >35 for DMSO were extrapolated using various methods.
N+H2
N-Me morpholine
NO2 O2N
+
7.38
R
NH2
(13.6) (23.5) 15.1 (25.5) (23.3) (17.2) (26.9) (24.8) (21.6)
O Me2N NNH2 NMe2
NH3
-9.3
NO2
R= H CH3 Ph CF3 NH2 (urea) OEt
O
(23.6) (20.0) 11 (14.2)
t-BuO O EtO O
N+Me3 O Me O O OMe O S S O Ph
X= H Ph SPh COCH3 SO2Ph
O Et Et O
9
(26.5) (19.8) (18.7) (13.3) (15.1)
X=
பைடு நூலகம்
CH2=CHCH3 PhH PhCH3 Ph2CH2 Ph3CH HCCH PhCCH XC6H4CH3 X= p-CN p-NO2 p-COPh
(26.6) (25.9) (24.9)
(26.1)
Me Me Et2N
20 15 H2 ~36
(20.1) (18.0)
(17.2) (18.2)
Me2N Me2N
S Me
Me
(25.7)
X= H CH3 Ph COCH3 COPh CO2Et CN F OMe OPh SPh SePh NPh2 N+Me3 NO2 SO2Ph
NH Ph O N H OH
1,2,3 triazole 8.88 (13.7) (NH)
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.
8.30
NH O
(14.7)
R
NH2
R= Me Ph
(17.3) (15.0)
Ac2NH SULFONAMIDE MeSO2NH2 PhSO2NH2 CF3SO2NH2 MeSO2NHPh 6.3
(17.9)
PROTONATED HETEROCYCLES
N
+
DBU (17.5) (16.1) (9.7) (12.9)
D.H. Ripin, D.A. Evans
Substrate pKa H2O (DMSO) Substrate pKa
pKa's of Nitrogen Acids
H2O (DMSO) Substrate pKa H2O (DMSO) IMIDES (7.9) (41)
O NH O O NSO2Ph
D.H. Ripin, D.A. Evans
Substrate
pKa's of CH bonds at Nitrile, Heteroaromatic, and Sulfur Substituted Carbon
Substrate pKa H2O (DMSO) SULFIDES PhSCH2X X= Ph CN COCH3 COPh NO2 SPh SO2Ph SO2CF3 POPh2 MeSCH2SO2Ph PhSCHPh2 (PhS)3CH (PrS)3CH
N+ OH
0.79
o-(CH3)3N C6H4 1.37 p-(CH3)3N+C6H4 3.43 p-OMeC6H4
O R OH
Ph
OH
4.47
SULFINIC & SULFONIC ACIDS
O Me S O Ph S O
PEROXIDES 4.25 3.02, 4.38 1.92, 6.23 11.5 8.2
Me Ph S+ CH2Ph S X
NC
X
Me
Ph
X=
H CH3 Ph COPh CONR2 CO2Et CN OPh N+Me3 SPh SO2Ph
(31.3) (32.5) (21.9) (10.2) (17.1) (13.1) (11.1) (28.1) (20.6) (20.8) (12.0)
-12.4
OH
OH
-7.8
Ph
+
OH OH
-6.2
Ph H Ph O+ H Me O+ CH3
-6.5
Me
-3.8
Me
O+ H H Me
+
-2.05 -2.2 -1.8
OXIMES & HYDROXAMIC ACIDS
N OH
O+ OH S
H
11.3 (20.1)
Me OH
Me
8.88 (13.7) (NH) (18.5)
O Ph N+
+
X= CH3 CH2NO2 CH2F CH2Cl CH2Br CH2I CHCl2 CCl3 CF3 H HO C6H5 o-O2NC6H4 m-O2NC6H4 p-O2NC6H4 o-ClC6H4 m-ClC6H4 p-ClC6H4
MeOH i-PrOH t-BuOH c-hex3COH CF3CH2OH (CF3)2CHOH C6H5OH m-O2NC6H4OH p-O2NC6H4OH p-OMeC6H4OH 2-napthol
+
Ph O Ph N O H N Me Ph
ALCOHOLS 15.7 (31.2) 15.54 (27.9) 16.5 (29.3) 17 24 12.5 (23.5) (17.9) 9.95 (18.0) 8.35 7.14 (10.8) 10.20 (19.1) (17.1) (29.4)
PROTONATED SPECIES
X= H Ph SPh
O S Ph X
(35.1) (29.0) (29.0)
11
X= H Ph SOPh
O Ph S CHPh2
(33) (27.2) (18.2) (24.5)
SULFONIUM (18.2) (16.3)
HETERO-AROMATICS (28.2) (30.1) (26.7)
D.H. Ripin, D.A. Evans
Substrate H2O H3O H2S HBr HCl HF HOCl HClO4 HCN HN3 HSCN H2SO3 H2SO4 H3PO4 HNO3 HNO2 H2CrO4 CH3SO3H CF3SO3H NH4Cl B(OH)3 HOOH
+
pKa's of Inorganic and Oxo-Acids
N+ H
AMINES HN3 NH3 i-Pr2NH TMS2NH PhNH2 Ph2NH NCNH2
NH Me Me
9.2 10.6 11.05
+
(10.5)
4.7
10.75 (9.00) 4.6 5.20 0.78
+
+
(3.6) (2.50)
38 (36 THF)) 26(THF) (30) (30.6) (25.0) (16.9) (44) (37) (26.5)
X= H CH3 t-Bu Ph CH=CH2 CH=CHPh CCH CCPh COPh COMe OPh N+Me3 CN NO2 SMe SPh SO2Ph PPh2
3
Ph
NHNH2
(20.95) (17.2) (26.1)
NH
PhSO2NHNH2 PhNHNHPh HYDROXAMIC ACID
+
NH3
+NH
+NH
3
(23.0)
N HN
(18.6)
Proton Sponge PhCN H
+
-9.0, 12.0 (--, 7.50)
O
(24.1)
NH O
12 (20.5)
S S H S Me O
Chem 206
pKa H2O (DMSO) NITRILES
Substrate
pKa H2O (DMSO)
Substrate pKa H2O (DMSO) SULFONES
O O S X
SULFOXIDES (30.8) (20.8) (18.7) (16.9) (11.8) (30.8) (20.3) (11.0) (24.9) (23.4) (26.7) (22.8) (31.3) (30.5) Me3S+=O
O Me
pKa H2O (DMSO)
Substrate
pKa H2O (DMSO) KETONES