Tablas De Pka Compuestos Orgánicos
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Publicado: 27 de enero de 2013
pKa's of Inorganic and Oxo-Acids
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 H2O (DMSO) 15.7 -1.7 7.00 -9.00 (0.9) -8.0 3.17 7.5 -10 9.4 4.72 4.00 1.9, 7.21 -3.0, 1.99 2.12, 7.21, 12.32 -1.3 3.29 -0.98, 6.50 -2.6 -14 9.24 9.23 11.6 (1.6) (0.3)
R OH
Chem 206
Substrate pKa H2O (DMSO)
Substrate
O X OHpKa
H2O (DMSO)
Substrate
pKa H2O (DMSO)
INORGANIC ACIDS (32)
CARBOXYLIC ACIDS HOH 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 2.45 3.44 2.94 3.83 3.99
Ph O Ph N O H N Me Ph
ALCOHOLS 15.7 15.5 16.5 17.0 24.0 12.5 9.3 9.95 8.4 7.1 10.2 (10.8) (19.1) (17.1) (23.5) (18.2) (18.0) (31.2) (27.9) (29.3) (29.4)
PROTONATED SPECIES
O Ph N+
+(1.8) (15)
(12.9) (7.9)
X= CH3 CH2NO2 CH2F CH2Cl CH2Br CH2I CHCl2 CCl3 CF3 H HO C6H5 o-O2NC6H4
MeOH i-PrOH
-12.4
OH
OH
t-BuOH c-hex3COH
CF3CH2OH (CF3)2CHOH C6H5OH
-7.8
Ph
+
OH OH CH3 H
Ph
-6.2
Ph
O+ H
-6.5
Me
m-O2NC6H4OH p-O2NC6H4OH p-OMeC6H4OH
2-napthol
Me
O+
-3.8
Me
O+ H H Me O+
+
-2.05 -2.2 -1.8
m-O2NC6H4 p-O2NC6H4 o-ClC6H4m-ClC6H4 p-ClC6H4
OXIMES & HYDROXAMIC ACIDS
N OH
H
OH S Me
11.3 (20.1) 8.88 (13.7) (NH) (18.5)
Me
OH
N+ OH Me Me N Me OH
0.79
(+1.63)
o-(CH3)3N+C6H4 1.37 p-(CH3)3N+C6H4 3.43 p-OMeC6H4
O
Ph
OH
(+5.55)
4.47
PEROXIDES
O O S O Ph S OH
SULFINIC & SULFONIC ACIDS -2.6 2.1
OH
R= H trans-CO2H
4.25 3.02, 4.38 1.92, 6.23
MeOOH CH3CO3H
11.5 8.2Me
cis-CO2H
*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
Substrate pKa H2O (DMSO) Substrate pKa
pKa's of Nitrogen Acids
H2O (DMSO) Substrate
O NH O
Chem 206
pKa H2O (DMSO)Substrate pKa H2O (DMSO)
PROTONATED NITROGEN N+H4 EtN+H
3
AMINES 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)
Me Me H2N N
IMIDES
O
HYDROXAMIC ACID & AMIDINES
O OH
9.2 10.6 11.05
(10.5)
8.30
NH O
(14.7) (17.9)
Ph
i-Pr2N+H2 Et3N+H PhN+H3
PhN+(Me) Ph2N+H2 2-napthal-N+H3 H2NN+H3 HON+H3Quinuclidine Morpholine
O N+ H
2H
N H NSO2Ph NH2
8.88 (13.7) (NH) R= Me Ph (17.3) (15.0)
10.75 (9.00) 4.6 5.20 0.78 4.16 8.12 5.96 11.0 (9.80) (3.6) (2.50)
Ac2NH
R
SULFONAMIDE (17.5) R = Me Ph (16.1) CF3 6.3 (9.7) MeSO2NHPh (12.9) RSO2NH2 GUANIDINIUM, HYRDAZONES,- IDES, & -INES
N+H2 Me2N O Ph
HETEROCYCLES
H N
(20.95)
H N N NH
(16.4)
(26.5)
H N N
(11.9)
NAMIDES & CARBAMATES
O
(23.0)
N
(13.6)
Ph
NNH2 Me
(21.6)
N+H2 8.36
R
NH2
N-Me morpholine
NO2 O2N
+
7.38
R= H (23.5) CH3 15.1 (25.5) Ph (23.3) CF3 (17.2) (urea) NH2 OEt (26.9) (24.8)
O
NMe2
(18.9)
NHNH2
N H X
X= O (24) X X= S (13.3) X= O (14.8) X= S (11.8)
HN
(18.6)
PhSO2NHNH2 PhNHNHPh
(17.2) (26.1)
N H N N H
+
N
NH N
(13.9) X= O(24.4) X= S (27.0)
NH3
-9.3
Et
O N H Ph
NO2
12 (20.5)
O NH Bn O
PROTONATED HETEROCYCLES
N
X H N S H
DABCO
H H3N+
N+ H N+
(21.6)
2.97, 8.82 (2.97, 8.93) 6.90, 9.95
3
DBU DMAP
Me2N R
+
(12) (estimate)
N H S
(19.8) (29.4)
Me
O NH
+NH 3
+NH
+NH
3
( )n
O
n= 1 (24.1) n= 2 (26.4)
(20.8)
O NH
NH
9.2
NH HN
+
H N+Me Me N
(16.5)
i-Pr
H
6.95
N
Proton Sponge PhCN+H
NMe 5.21 (3.4) H 4.95 (0.90) O NH NH N (12.1) N + (18.4) 6.75 (4.46) H Me R -10 0.72 *Values 14 for water and >35 for DMSO were extrapolated using various methods.
-9.0, 12.0 (--, 7.50)
(15)
O
O
+
R= H (PPTS) t-Bu Me Cl, H
(24)
Me
N+
i-Pr
For a comprehensive compilation of Bordwell pKa data see:...
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 H2O (DMSO) 15.7 -1.7 7.00 -9.00 (0.9) -8.0 3.17 7.5 -10 9.4 4.72 4.00 1.9, 7.21 -3.0, 1.99 2.12, 7.21, 12.32 -1.3 3.29 -0.98, 6.50 -2.6 -14 9.24 9.23 11.6 (1.6) (0.3)
R OH
Chem 206
Substrate pKa H2O (DMSO)
Substrate
O X OHpKa
H2O (DMSO)
Substrate
pKa H2O (DMSO)
INORGANIC ACIDS (32)
CARBOXYLIC ACIDS HOH 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 2.45 3.44 2.94 3.83 3.99
Ph O Ph N O H N Me Ph
ALCOHOLS 15.7 15.5 16.5 17.0 24.0 12.5 9.3 9.95 8.4 7.1 10.2 (10.8) (19.1) (17.1) (23.5) (18.2) (18.0) (31.2) (27.9) (29.3) (29.4)
PROTONATED SPECIES
O Ph N+
+(1.8) (15)
(12.9) (7.9)
X= CH3 CH2NO2 CH2F CH2Cl CH2Br CH2I CHCl2 CCl3 CF3 H HO C6H5 o-O2NC6H4
MeOH i-PrOH
-12.4
OH
OH
t-BuOH c-hex3COH
CF3CH2OH (CF3)2CHOH C6H5OH
-7.8
Ph
+
OH OH CH3 H
Ph
-6.2
Ph
O+ H
-6.5
Me
m-O2NC6H4OH p-O2NC6H4OH p-OMeC6H4OH
2-napthol
Me
O+
-3.8
Me
O+ H H Me O+
+
-2.05 -2.2 -1.8
m-O2NC6H4 p-O2NC6H4 o-ClC6H4m-ClC6H4 p-ClC6H4
OXIMES & HYDROXAMIC ACIDS
N OH
H
OH S Me
11.3 (20.1) 8.88 (13.7) (NH) (18.5)
Me
OH
N+ OH Me Me N Me OH
0.79
(+1.63)
o-(CH3)3N+C6H4 1.37 p-(CH3)3N+C6H4 3.43 p-OMeC6H4
O
Ph
OH
(+5.55)
4.47
PEROXIDES
O O S O Ph S OH
SULFINIC & SULFONIC ACIDS -2.6 2.1
OH
R= H trans-CO2H
4.25 3.02, 4.38 1.92, 6.23
MeOOH CH3CO3H
11.5 8.2Me
cis-CO2H
*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
Substrate pKa H2O (DMSO) Substrate pKa
pKa's of Nitrogen Acids
H2O (DMSO) Substrate
O NH O
Chem 206
pKa H2O (DMSO)Substrate pKa H2O (DMSO)
PROTONATED NITROGEN N+H4 EtN+H
3
AMINES 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)
Me Me H2N N
IMIDES
O
HYDROXAMIC ACID & AMIDINES
O OH
9.2 10.6 11.05
(10.5)
8.30
NH O
(14.7) (17.9)
Ph
i-Pr2N+H2 Et3N+H PhN+H3
PhN+(Me) Ph2N+H2 2-napthal-N+H3 H2NN+H3 HON+H3Quinuclidine Morpholine
O N+ H
2H
N H NSO2Ph NH2
8.88 (13.7) (NH) R= Me Ph (17.3) (15.0)
10.75 (9.00) 4.6 5.20 0.78 4.16 8.12 5.96 11.0 (9.80) (3.6) (2.50)
Ac2NH
R
SULFONAMIDE (17.5) R = Me Ph (16.1) CF3 6.3 (9.7) MeSO2NHPh (12.9) RSO2NH2 GUANIDINIUM, HYRDAZONES,- IDES, & -INES
N+H2 Me2N O Ph
HETEROCYCLES
H N
(20.95)
H N N NH
(16.4)
(26.5)
H N N
(11.9)
NAMIDES & CARBAMATES
O
(23.0)
N
(13.6)
Ph
NNH2 Me
(21.6)
N+H2 8.36
R
NH2
N-Me morpholine
NO2 O2N
+
7.38
R= H (23.5) CH3 15.1 (25.5) Ph (23.3) CF3 (17.2) (urea) NH2 OEt (26.9) (24.8)
O
NMe2
(18.9)
NHNH2
N H X
X= O (24) X X= S (13.3) X= O (14.8) X= S (11.8)
HN
(18.6)
PhSO2NHNH2 PhNHNHPh
(17.2) (26.1)
N H N N H
+
N
NH N
(13.9) X= O(24.4) X= S (27.0)
NH3
-9.3
Et
O N H Ph
NO2
12 (20.5)
O NH Bn O
PROTONATED HETEROCYCLES
N
X H N S H
DABCO
H H3N+
N+ H N+
(21.6)
2.97, 8.82 (2.97, 8.93) 6.90, 9.95
3
DBU DMAP
Me2N R
+
(12) (estimate)
N H S
(19.8) (29.4)
Me
O NH
+NH 3
+NH
+NH
3
( )n
O
n= 1 (24.1) n= 2 (26.4)
(20.8)
O NH
NH
9.2
NH HN
+
H N+Me Me N
(16.5)
i-Pr
H
6.95
N
Proton Sponge PhCN+H
NMe 5.21 (3.4) H 4.95 (0.90) O NH NH N (12.1) N + (18.4) 6.75 (4.46) H Me R -10 0.72 *Values 14 for water and >35 for DMSO were extrapolated using various methods.
-9.0, 12.0 (--, 7.50)
(15)
O
O
+
R= H (PPTS) t-Bu Me Cl, H
(24)
Me
N+
i-Pr
For a comprehensive compilation of Bordwell pKa data see:...
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