常见有机物pKa表
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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
O Me
pKa H2O (DMSO)
Substrate
pKa H2O (DMSO) KETONES
Substrate
HYDROCARBONS (Me)3CH (Me)2CH2 CH2=CH2 CH4 53 51 50 48 46 43 43 41 (43) (56)
24.5 (30.3)
Me
O X X
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
X= H CH3 t-Bu Ph CH=CH2 CH=CHPh CCH CCPh COPh COMe OPh N+Me3 CN NO2 SMe SPh SO2Ph PPh2
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
Substrate
O Xபைடு நூலகம்OH
Chem 206
Substrate pKa H2O (DMSO)
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) (12.9) (7.9) (1.8) (15) (32)
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=
CH2=CHCH3 PhH PhCH3 Ph2CH2 Ph3CH HCCH PhCCH XC6H4CH3 X= p-CN p-NO2 p-COPh
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
有机物pka表 values>14 dmsowere extrapolated using various methods. 0.79 sulfinic sulfonicacids peroxides pka (dmso) (dmso) pka pka (dmso) pka's oxo-acids8.2 11.5 12.5 15.5 15.7 (11.1) (12.3) (1.6) (0.3) -14 (7.9) (12.9) (15) (1.8) (0.9) (32) (dmso) cis-co 3.6,10.3 3.77 -0.25 0.65 1.29 -8.0 11.6 -3.0, 1.99 1.9, 7.21 4.00 2.12, 7.21, 12.32 7.00 -1.7 15.7 -1.3 3.29 4.72 9.24 3.17 -0.98, 6.50 9.4 -2.6 -10 7.5 -9.00 9.23 inorganic acids chem 206 substrate substrate 1.92,6.23 -12.4 -7.8 -6.2 -3.8 -2.05 -2.2 -2.6 2.1 -1.8-6.5 1.682.66 2.86 2.86 3.12 4.76 4.2 o-o 2.172.45 3.44 2.94 3.83 3.99 1.37 p-(ch 3.434.47 4.25 3.02, 4.38 substrate substrate (13.7) (18.5) protonated species carboxylic acids (31.2) (27.9) (29.3) (23.5) (18.2) (29.4) 10.2 7.1 8.4 p-omec ohp-o ohm-o oh9.95 (18.0) 2-napthol (17.1) (10.8) (19.1) alcohols 16.5 17.0 c-hex coh24.0 oximes hydroxamicacids 8.88 11.3 (20.1) pka phph phoh ohph ohph oh oh ph ph ch ohme me meph comprehensivecompilation bordwellpka data see: /areas/reich/pka
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)
-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)
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.
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)
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)
(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
Chem 206
Substrate pKa H2O (DMSO) AMIDINES
PROTONATED NITROGEN N+H4 EtN+H3 i-Pr2N H2 Et3N+H PhN H3 PhN+(Me)2H Ph2N H2 2-napthal-N H3 H2NN H3 HON H3 Quinuclidine Morpholine
+
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
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
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
Me Me
(44)
EtO
19-20 (27.1) (28.3)
i-Pr O i-Pr
H OMe NMe2 Br CN
(24.7) (25.7) (27.5) (23.8) (22.0)
O
13
(15.7)
n n= 4 5 6 7 8 (25.1) (25.8) (26.4) (27.7) (27.4)
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)
R NH R
+
(12) (estimate)
+
4.16 8.12 5.96 11.0 (9.80)
H2N N
N H
+
DMAP
Me2N
+
TMP
NH Me Me
NH
9.2
NH HN
+
6.95
+
O
N+H2 8.36
AMIDES & CARBAMATES
O
GUANIDINIUM, HYRDAZONES,- IDES, & -INES
pKa
H2O (DMSO)
Substrate
pKa H2O (DMSO)
INORGANIC ACIDS
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
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)
MeO
33.5 (32.2) 31.5 (30.6) 24 (28.8) 23
MeO
(27.7) (20.9)
t-Bu O Ph Me
(26.3)
i-Pr O Ph X
[30.2 (THF)]
LiO
AMIDES (30.8) (20.4) (26.9)
Me2N Me2N O Ph O SPh O N+Me3 O N O CN O
(13.9)
D.H. Ripin, D.A. Evans
Substrate
pKa's of CH bonds in Hydrocarbons and Carbonyl Compounds
Substrate pKa H2O (DMSO) ESTERS
O t-BuO Me Ph
Chem 206
pKa H2O (DMSO)
(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)
O
(28.1)
O
(29.0)
O
(25.5)
O
(32.4)
Me Me
*Values <0 for H2O and DMSO, and values >14 for water and >35 for DMSO were extrapolated using various methods.
-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.
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
O Me
pKa H2O (DMSO)
Substrate
pKa H2O (DMSO) KETONES
Substrate
HYDROCARBONS (Me)3CH (Me)2CH2 CH2=CH2 CH4 53 51 50 48 46 43 43 41 (43) (56)
24.5 (30.3)
Me
O X X
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
X= H CH3 t-Bu Ph CH=CH2 CH=CHPh CCH CCPh COPh COMe OPh N+Me3 CN NO2 SMe SPh SO2Ph PPh2
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
Substrate
O Xபைடு நூலகம்OH
Chem 206
Substrate pKa H2O (DMSO)
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) (12.9) (7.9) (1.8) (15) (32)
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=
CH2=CHCH3 PhH PhCH3 Ph2CH2 Ph3CH HCCH PhCCH XC6H4CH3 X= p-CN p-NO2 p-COPh
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
有机物pka表 values>14 dmsowere extrapolated using various methods. 0.79 sulfinic sulfonicacids peroxides pka (dmso) (dmso) pka pka (dmso) pka's oxo-acids8.2 11.5 12.5 15.5 15.7 (11.1) (12.3) (1.6) (0.3) -14 (7.9) (12.9) (15) (1.8) (0.9) (32) (dmso) cis-co 3.6,10.3 3.77 -0.25 0.65 1.29 -8.0 11.6 -3.0, 1.99 1.9, 7.21 4.00 2.12, 7.21, 12.32 7.00 -1.7 15.7 -1.3 3.29 4.72 9.24 3.17 -0.98, 6.50 9.4 -2.6 -10 7.5 -9.00 9.23 inorganic acids chem 206 substrate substrate 1.92,6.23 -12.4 -7.8 -6.2 -3.8 -2.05 -2.2 -2.6 2.1 -1.8-6.5 1.682.66 2.86 2.86 3.12 4.76 4.2 o-o 2.172.45 3.44 2.94 3.83 3.99 1.37 p-(ch 3.434.47 4.25 3.02, 4.38 substrate substrate (13.7) (18.5) protonated species carboxylic acids (31.2) (27.9) (29.3) (23.5) (18.2) (29.4) 10.2 7.1 8.4 p-omec ohp-o ohm-o oh9.95 (18.0) 2-napthol (17.1) (10.8) (19.1) alcohols 16.5 17.0 c-hex coh24.0 oximes hydroxamicacids 8.88 11.3 (20.1) pka phph phoh ohph ohph oh oh ph ph ch ohme me meph comprehensivecompilation bordwellpka data see: /areas/reich/pka
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)
-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)
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.
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)
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)
(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
Chem 206
Substrate pKa H2O (DMSO) AMIDINES
PROTONATED NITROGEN N+H4 EtN+H3 i-Pr2N H2 Et3N+H PhN H3 PhN+(Me)2H Ph2N H2 2-napthal-N H3 H2NN H3 HON H3 Quinuclidine Morpholine
+
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
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
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
Me Me
(44)
EtO
19-20 (27.1) (28.3)
i-Pr O i-Pr
H OMe NMe2 Br CN
(24.7) (25.7) (27.5) (23.8) (22.0)
O
13
(15.7)
n n= 4 5 6 7 8 (25.1) (25.8) (26.4) (27.7) (27.4)
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)
R NH R
+
(12) (estimate)
+
4.16 8.12 5.96 11.0 (9.80)
H2N N
N H
+
DMAP
Me2N
+
TMP
NH Me Me
NH
9.2
NH HN
+
6.95
+
O
N+H2 8.36
AMIDES & CARBAMATES
O
GUANIDINIUM, HYRDAZONES,- IDES, & -INES
pKa
H2O (DMSO)
Substrate
pKa H2O (DMSO)
INORGANIC ACIDS
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
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)
MeO
33.5 (32.2) 31.5 (30.6) 24 (28.8) 23
MeO
(27.7) (20.9)
t-Bu O Ph Me
(26.3)
i-Pr O Ph X
[30.2 (THF)]
LiO
AMIDES (30.8) (20.4) (26.9)
Me2N Me2N O Ph O SPh O N+Me3 O N O CN O
(13.9)
D.H. Ripin, D.A. Evans
Substrate
pKa's of CH bonds in Hydrocarbons and Carbonyl Compounds
Substrate pKa H2O (DMSO) ESTERS
O t-BuO Me Ph
Chem 206
pKa H2O (DMSO)
(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)
O
(28.1)
O
(29.0)
O
(25.5)
O
(32.4)
Me Me
*Values <0 for H2O and DMSO, and values >14 for water and >35 for DMSO were extrapolated using various methods.
-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.