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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
(31.2) O
HOH 15.7
N+ -12.4
H3O+ -1.7 X OH MeOH 15.5 (27.9) Ph OH
X= CH3 4.76 (12.3) i-PrOH (29.3)
+
OH
H2S 7.00 16.5
CH2NO2 1.68 -7.8
t-BuOH 17.0 (29.4) Ph OH
HBr -9.00 (0.9) CH2F 2.66 +
c-hex3COH OH
HCl -8.0 (1.8) CH2Cl 2.86 24.0
-6.2
CH2Br 2.86 CF3CH2OH 12.5 (23.5) Ph CH3
HF 3.17 (15)
CH2I 3.12 (CF3)2CHOH 9.3 (18.2) H
HOCl 7.5 CHCl2 1.29 O+ -6.5
C6H5OH 9.95 (18.0) Ph Me
HClO4 -10 CCl3 0.65
CF3 -0.25 m-O2NC6H4OH 8.4 H

HCN 9.4 (12.9) O+ -3.8
H 3.77 p-O2NC6H4OH 7.1 (10.8) Me Me
HN3 4.72 (7.9) HO 3.6, 10.3 p-OMeC6H4OH 10.2 (19.1) O+ H -2.05
C6H5 4.2 (11.1)
HSCN 4.00 2-napthol (17.1) H
o-O2NC6H4 2.17 O+ -2.2
H2SO3 1.9, 7.21 m-O2NC6H4 2.45 OXIMES & HYDROXAMIC ACIDS Me
+
H
OH
p-O2NC6H4 3.44 OH
H2SO4 -3.0, 1.99 N S -1.8
o-ClC6H4 2.94 11.3 (20.1) Me Me
H3PO4 2.12, 7.21, Ph Ph
12.32 m-ClC6H4 3.83 O
N+ OH 0.79 (+1.63)
HNO3 -1.3 OH 8.88 (13.7)
p-ClC6H4 3.99 Ph N (NH)
O H Me
HNO2 3.29 o-(CH3)3N+C6H4 1.37
OH Me N OH (+5.55)
p-(CH3)3N+C6H4 3.43 Ph N (18.5)
H2CrO4 -0.98, 6.50 Me
p-OMeC6H4 4.47 Me
CH3SO3H -2.6 (1.6) SULFINIC & SULFONIC ACIDS
O
PEROXIDES
CF3SO3H -14 (0.3)
R OH O O
NH4Cl 9.24 S -2.6
R= H 4.25 MeOOH 11.5 Me OH
B(OH)3 9.23 trans-CO2H 3.02, 4.38 O
CH3CO3H 8.2
S 2.1
HOOH 11.6 cis-CO2H 1.92, 6.23 Ph 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

0 O R Me O 5.30 NH (14.2 6.20 (2.78 NH (44) Ph (16.7 (7.4) NO2 Et N N H (21. For a comprehensive compilation of Bordwell pKa data see: http://www.36 O (18.3) H Ph NHNH2 X N-Me morpholine 7.95 n= 2 (26.6) Ph2NH (25.6 NH 8. & -INES N NH (23.H.9) Ph (15.5) Me2N NMe2 Ph Me X= O (24) N CH3 15.1 (25.50) NCNH2 (16.97..8) N + OEt (24.16 Me MeSO2NHPh (12. Ripin.97.5) X= O (24.12 H2N N (26. H i-Pr *Values <0 for H2O and DMSO.1) N (13.9) HON+H3 5.wisc. 8.4) N+ H 6.5) 8.3 (9.9) O2N NH3 -9.4) 2-napthal-N+H3 4.7) Ph N i-Pr2NH (36 THF)) H i-Pr2N+H2 11.6) NNH2 (21. and values >14 for water and >35 for DMSO were extrapolated using various methods.9) HETEROCYCLES 2H NH (37) RSO2NH2 R = Me (17.2) NO2 PhSO2NHNH2 (17.05 TMS2NH 26(THF) (30) NSO2Ph O O R= Me (17.82 + H DABCO N+ (2.2) X= O (14.93) O Bn N O H S S H n= 1 (24.9) O O O N+H4 9.9) NH PhNHNHPh X= S (11. 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 HYDROXAMIC ACID & AMIDINES HN3 4.3) (18.4) O NH + NH N N+ 3 ( )n Me2N NH 9.00) PhNH2 (30.96 HYRDAZONES.5) Ph2N+H2 0.9) H2NN+H3 8.6) O NH N X= S (27.5) H N GUANIDINIUM.5) H3N+ NH + +NH 6.8) 2.0 (9.88 (13.2 11/4/05 1:43 PM .1) (4.8) (26.50) (15) (24) O 4. N (11. 7.0) H AMIDES & CARBAMATES N+H2 N Quinuclidine N+ 11.90) + t-Bu H H O NH NH N (12.7) N N (16.95 Me Me +NH +NH HN 3 3 i-Pr -9.6 (3.6) Ac2NH (17.46) N + (18.4) R= H (PPTS) NMe N Proton Sponge (--.0) R NH2 PhN+H3 4.0) Me Me SULFONAMIDE PhN+(Me) 5.4) H (16.72 Cl.75 Me Me Me PhCN+H -10 R 0.htm pKa Table. 8.8) DMAP H (29.75 (9. D.edu/areas/reich/pkatable/index.3) Et3N+H 10.6) O R= H (23.A.0) H (12) (estimate) N N N+ H DBU (19.D.95) H Me CF3 6.95 (0.9) N X X= S (13.0.80) (13.90.1) H (20.5) HN Morpholine O N+H2 8.38 CF3 (17.8) (urea) NH2 (26.6) R NH2 Ph (23. 9.chem. 12.3 N O O PROTONATED HETEROCYCLES H X Ph 12 (20.2 (10.IDES.1) (20.21 (3.7) NH3 38 (41) OH (NH) EtN+H 3 10.

9) (25.8) 46 EtO SO2Ph (12. D.2) Me2N O COPh (13.0) p-COPh (26.4) 15 (18.6) Ph (19.3 11/4/05 1:44 PM .3) (29.7) (28.3) X (Me)2CH2 51 t-BuO Me Me X O (26.wisc.4) (28.1) X= p-CN (30.4) HCCH 24 O O 7 (27.1) SPh (16.edu/areas/reich/pkatable/index.6) S Ph i-Pr 6 (26.6) NPh2 (20.8) X LiO Ph XC6H4CH3 X= H (24.5) (20.5 (30. and values >14 for water and >35 for DMSO were extrapolated using various methods.5) Br O O O CN (22.3) 5 Ph3CH 31.9) (25.2) 19-20 (27.3) n PhCH3 (43) i-Pr O i-Pr 41 MeO OMe O (27.1) N (17.6) (26.5 (32.htm pKa Table.7) SO2Ph (11.85) O N+Me3 OMe (25.7) O SPh OMe CH4 48 (56) NMe2 (27.0) CH2=CHCH3 43 (44) 11 (14.2) N+Me3 (14.5) Me Me Et2N O OPh (21.1) (24.9) O SPh CN (10.8) MeO (26.4) Me2N Me *Values <0 for H2O and DMSO.9) (22.A.1) S (20.0) COCH3 9 (13.7) Ph [30.7) Ph2CH2 33.5 (30. D.3) N+Me3 (23.2) t-Bu O Me n= 4 (25.1) O EtO Me Et Et O PhH 43 O O 13 (15.7) p-NO2 (20.5) X= H CH2=CH2 Ph (23.7) AMIDES CH3 (24.4) PhCCH 23 (28.0) (18.9) CN 20 (20.6) Me2N Me NO2 (7.6) Ph (17.chem.3) O O O (32. 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.H.2 (THF)] 8 (27.2) Me Me Me2N O F (21.8) O O (26.4) Ph COCH3 (14.7) (25. For a comprehensive compilation of Bordwell pKa data see: http://www. Ripin.8) X= H (24.7) Me Me S H2 ~36 (25.2) SePh (18.7) 50 t-BuO (18.

0) (18.4) COPh (30.8) S PhSCH=CHCH2SPh (26.2) (22.8) S X Ph (23.0) S (22.4 11/4/05 1:44 PM .5) HETERO-AROMATICS S SPh S+ (30.9) SPh (20.5) N+Me3 (20.2) H Ph SULFIMIDES & SULFOXIMINES O O N (PhS)2CHPh (23.7) O NTs (18.8) Ph (24.6) Me Me N X= Ph (30.A.4) OPh (28.0) N+Me2 S (26.9) O t-Bu (31.2) CO2Et (13.1) Me SMe (23.3) S (20.2) NO2 (7. 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 (30.4) CN (12.3) Me3S+=O (18. O (23.8) Me Ph X= H (31.3) (20.1) S S R= Me (27.4) S (24. Ripin.8) Ph CO2Me (20.1) O CCPh COPh (11.5) CONR2 (17.0) Ph CH2Cl S BuSH 10-11 (17.5) Ph CH2Ph SO2Ph (12.0) X= H CH3 (32.3) PhSH ≈7 (10.3) *Values <0 for H2O and DMSO.2) NO2 (11. Evans pKa's of CH bonds at Nitrile. pKa Table.4) CF3 i-Pr S Ph (30.7) i-Pr (30.0) (21. Heteroaromatic.7) SPh (29.8) (PhS)3CH (22.9) SOPh (17. and values >14 for water and >35 for DMSO were extrapolated using various methods.2) (28.3) CN (20.5) CF3 Me CN (19.9) COPh (16.7) O O (26.6) PhSCHPh2 (26.2) Ph (10.0) SO2Ph (12.2) S S PPh2 (20.8) SPh Ph CH=CH2 (22.0) (PrS)3CH (31.5) Ph CHPh2 COMe (12.1) MeSCH2SO2Ph (23.5) Me (16.7) OPh (27.8) X= H (35. D.3) (33) CF3 i-Pr N+ (25.2) R= Me S O O Ph Me Et (24.6) O.8) S S (24.8) SULFONIUM N+Me3 (19.5) X= H (33) CH=CHPh (20.1) Ph (27.1) SO2Ph (20.D.0) CH3 (31.8) CN 11 (11.9) Ph Me O O O t-Bu O NTs (32.5) COCH3 (18.3) NTs Ph CHPh2 S (30.0) (PhSO2)2CH2Me (14.2) (22.1) (29.0) Ph (29.H.1) Ph Me O O RSCH2CN O NMe S (21.1) X S O O N Ph Ph R (31.6) (14.7) Et Et Ph (30.1) SO2CF3 (11.2) CCH POPh2 (24.

3095 (1978) O O JOC 43.htm pKa Table.2) MeO (22.9) JACS 105.wisc. P.7 R= CH3 ≈10 (17.0) Ph2PCH2PPh2 (29.4) CHMe2 (16. 3224 (1982) 5 (16.7) Et3P+H 9. Chem. D.2) JOC 47. 4327 (1981) CN (16. 2504 (1982) 6 (17. 3rd Ed.2) JACS 97. 7160 (1975) MeOCH2SO2Ph (30. 1989 CO2Et (20.8) JOC 42.chem.3) 4 (17.6) Ph Ph SO2Ph (19. JOC 1991. 56. 3325 (1980) PhSe (18.edu/areas/reich/pkatable/index. 6188 (1983) Ph3P+CH3 (22. 326 (1977) SELENIDES PHOSPONATES & JOC 43.D. For a comprehensive compilation of Brodwell pKa data see: http://www.6) (EtO)2P X Ph JOC 45.9) Acc.85) JOC 41.. Res.1) Ph3P+i-Pr (21.7) JOC 42.6) (26.8) Unpublished results of F. 3113 (1978) PHOSPHINE OXIDES O2N JOC 43.9) JOC 41. H. 456 (1988) PhSeCH=CHCH2SePh (27.8) (15. 5705 (1988) COPh Streitwieser.4) (PhSe)2CH2 (31. 2786 (1976) Ph3P+CH2COPh (6. 442 (1975) PhOCH2SO2Ph (27. 1764 (1978) n JOC 45. 1817 (1977) CH2SO2Ph (7.0) PhSeCH2Ph (31.1 CH2Me (16. 1885 (1976) O JOC 41.2) CH2Ph (12.0) Cl (26. 3884 (1980) PhSeCHPh2 (27. 1883 (1976) PhOCH2CN (28. 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 DMSO: P+H4 -14 RNO2 CH3OPh (49) JACS 97. 2508 (1976) Ph Ph3P+CH2CN (7.9) See cited website below for additional data CONEt2 (24. Ripin.8) JOC 46. and values >14 for water and >35 for DMSO were extrapolated using various methods. 632 (1981) CO2Et (18.2) JOC 41.3) Unpublished results of W. A.1) JOC 42. 321 (1977) CH2COPh (7. Chem.0) CH2SPh (11. 7007 (1975) MeP+H3 2. 21.5) n= 3 JOC 46. 3305 (1980) X= Ph (27.6) JOC 47. March (1985) Me3N+CH2X CN (16.5 11/4/05 1:45 PM . Bordwell O 7 Ph2P X Water: AMMONIUM IMINES X= SPh (24. N Ph J.9) JOC 45.4) PHOSPHINES Oxime ethers are ~ 10 pka units less THF: (14.2) SiMe3 (28.9) Ph2PCH2SO2Ph (20.2) CH2Bn (16.6) acidic than their ketone counterparts JACS 110.7) JACS 97.2) *Values <0 for H2O and DMSO.9) Advanced Org.9) (24. Jencks X= CN (20.

ACR. DMSO Acidities of Common Heterocycles Bordwell.4 16.8 29. 456 Bordwell http://www.3 14.0 Me O S Me Me S Me S N N H H H H N+ N S N Me N+ N+ H N N Me Me H H Me Me Me 13.htm N N N N N N N N N N N N N H H H H H H 23.6 16.5 18. 1988.8 18.8 11.cdx 11/4/05 1:45 PM .4 24.wisc.0 19.6.4 24 Pka Table.0 O O O O O O O N N N N N O N O H H H H H H 24.8 15.9 11.4 13.1 26.9 18.chem.0 20. 21.0 12.edu/areas/reich/pkatable/index.