D.H. Ripin, D.A. Evans *Values 14 for water and 35 for DMSO were extrapolated using various methods. 0.79 SULFINIC & SULFONIC ACIDS PEROXIDES H2OpKa(DMSO)(DMSO)pKaH2OH2OpKa(DMSO) pKa's of Inorganic and Oxo-Acids 8.2 11.5 CH3CO3H MeOOH 12.5 15.54 15.7 (11.1) (12.3) (1.6) (0.3)CF3SO3H-14 (7.9) (12.9) (15) (1.8) (0.9) (32) (DMSO) (CF3)2CHOH CF3CH2OH t-BuOH MeOH HOH cis-CO2H trans-CO2H HR= 3.6, 10.3HO 3.77H -0.25CF3 0.65CCl3 1.29CHCl2 -8.0 11.6 HOOH -3.0, 1.99H2SO4 1.9, 7.21H2SO3 4.00 HSCN 2.12, 7.21, 12.32 H3PO4 7.00H2S -1.7 15.7 H3O+ H2O -1.3 HNO3 3.29 HNO2 4.72HN3 9.24 NH4Cl 3.17 -0.98, 6.50 9.4 -2.6 -10 7.5 -9.00 9.23 H2CrO4 HCN CH3SO3H HClO4 HOCl HF HCl HBr B(OH)3 INORGANIC ACIDS Chem 206 SubstrateSubstrate + + 1.92, 6.23 -12.4 -7.8 -6.2 -3.8 -2.05 -2.2 -2.6 2.1 + -1.8 -6.5 X= CH2NO2 CH2F CH2Cl CH2Br CH2I 1.68 2.66 2.86 2.86 3.12 CH34.76 4.2 o-O2NC6H4 m-O2NC6H4 p-O2NC6H4 o-(CH3)3N+C6H4 p-OMeC6H4 p-ClC6H4 o-ClC6H4 m-ClC6H4 2.17 2.45 3.44 2.94 3.83 3.99 1.37 p-(CH3)3N+C6H43.43 4.47 C6H5 4.25 3.02, 4.38 SubstrateSubstrate (13.7) (18.5) PROTONATED SPECIESCARBOXYLIC ACIDS (31.2) (27.9) (29.3) (23.5) (17.9) (29.4) i-PrOH C6H5OH 10.20 7.14 8.35 p-OMeC6H4OH p-O2NC6H4OH m-O2NC6H4OH 9.95 (18.0) 2-napthol(17.1) (10.8) (19.1) ALCOHOLS 16.5 17 c-hex3COH 24 OXIMES & HYDROXAMIC ACIDS 8.88 (NH) 11.3(20.1) pKaH2O O OHR PhPh N OH N H Ph OH N+ O OH O+ H HMe N OH Ph O Me O OHX Me O+ Me N+ O OHPh OH OHPh PhCH3 OH O+ H H Me S OH OO Ph S OH O S OH MeMe O+ H MePh D.H. Ripin, D.A. Evans *Values 14 for water and 35 for DMSO were extrapolated using various methods. 38 (12) (estimate) pKa's of Nitrogen Acids H2O (DMSO) Chem 206 SubstrateSubstrateSubstrate pKa Substrate DABCO DBU Et3N+H i-Pr2N+H2 i-Pr2NH EtN+H3 TMS2NH N+H4 NH3 TMP (41) (36 THF)) (37) (30) (10.5)9.2 10.6 11.05 10.75 PhNH2 Ph2NH (30.6) (25.0) PhN+H3 Ph2N+H2 4.6 0.78 2-napthal-N+H3 4.16 (3.6) H2NN+H3 HON+H3 8.12 5.96 + -9.3 H (PPTS) 5.21 (3.4) + DMAP 9.2 + 4.95 (0.90) PhN+(Me)2H 5.20(2.50) R= t-Bu Me6.75 (4.46) + 6.95 N-Me morpholine7.38 Morpholine8.36 2.97, 8.82 (2.97, 8.93) (9.00) 6.90, 9.95 Quinuclidine11.0 (9.80) Proton Sponge -9.0, 12.0 (--, 7.50) ++ (20.5) 12 + (20.95) (18.6)(23.0) (44) NCNH2(16.9) (26.5) 1,2,3 triazole (13.9) R=H CH3 Ph CF3 NH2 (urea) OEt (23.5) (25.5) (23.3) (17.2) (26.9) (24.8) 15.1 (21.6) Ac2NH(17.9) Cl, H 0.72 (17.0) (24.1) (14.7) 8.30 (NH) 8.88 (13.7) (13.6) PhSO2NHNH2 (21.6) (18.9) (17.2) PhNHNHPh (26.1) AMIDES & CARBAMATES PROTONATED NITROGENAMINES PhSO2NH2 MeSO2NH2 CF3SO2NH2 (17.5) (16.1) 6.3 (9.7) HN34.7(7.9) PhCN+H-10 MeSO2NHPh(12.9) IMIDES SULFONAMIDE HYRDAZONES,- IDES, & -INES HYDROXAMIC ACID AMIDINES HETEROCYCLES PROTONATED HETEROCYCLES R=Me (17.3) Ph (15.0) pKa(DMSO)H2OH2O (DMSO)pKapKa(DMSO)H2O GUANIDINIUM, N+ N+ N N H NH Me Me Me Me O2N NO2 NO2 NH3 NH HN H NHMe2N NH R R H H3N+ +NH3 NH3NH3 NHO O Bn O N+ H N+H2 H N HN N NH H2NN N N NH RNH2 O NH O N H Et Ph N H O NH O NH O OO O NH O N H Ph OH Ph Me2NNMe2 N+H2 Me NNH2 O NHNH2Ph NSO2Ph NH2R 26(THF) D.H. Ripin, D.A. Evans 19-20 9 13 11 24.5 ~36H2 *Values 14 for water and 35 for DMSO were extrapolated using various methods. HCCH H2O (DMSO) SubstrateSubstrateSubstrate pKaSubstrate AMIDES HYDROCARBONS pKa(DMSO)H2OH2O (DMSO)pKapKa(DMSO)H2O CH4 CH2=CHCH3 PhH CH2=CH2 PhCH3 Ph2CH2 Ph3CH (56) (44) (43) (32.2) (30.6) (Me)3CH 53 (Me)2CH2 51 50 48 43 46 41 33.5 31.5 43 24 PhCCH23 (28.8) XC6H4CH3 X=p-CN p-NO2 p-COPh (30.8) (20.4) (26.9) (26.1) (18.0) (20.1) 15 20 X=H Ph SPh COCH3 SO2Ph (26.5) (19.8) (18.7) (13.3) (15.1) (27.1) (28.3) (27.7) (26.3) X=H CH3 COCH3 COPh CO2Et CN OMe NPh2 (22.85) N+Me3 NO2 SPh OPh SO2Ph SePh (24.7) (24.4) (17.7) (12.7) (13.3) (22.7) (10.2) (21.6) (20.3) (14.6) (7.7) (16.9) (21.1) (11.4) (18.6) X=H OMe NMe2 Br CN (24.7) (25.7) (27.5) (23.8) (22.0) n= 8 7 6 5 4 (27.4) (27.7) (26.4) (25.8) (25.1) (29.0) (28.1) (25.5) (32.4) (30.3) (23.6) (20.0) (14.2) (15.7) (20.9) (26.6) (25.9) (24.9) (17.2) (25.7) (18.2) F Ph KETONESESTERS n [30.2 (THF)] pKa's of CH bonds in Hydrocarbons and Carbonyl Compounds Me Me Me Me Me O X O EtEt S i-Pri-Pr O O Met-Bu Ph X Phi-Pr O O LiO O Ph Me O X O O O O O Me Me t-BuO O Met-BuO O Ph EtO O N+Me3 O EtOMe O O OMeMeO O O MeO S N+Me3 O Et2N Ph O Me2N Me2N O SPh N O CN Me2NMe S O MeMe2N O Chem 206 D.H. Ripin, D.A. Evans 11 (10.3) (17.0) ≈7 10-11 PhSH BuSH *Values 14 for water and 35 for DMSO were extrapolated using various methods. (16.3) (18.2)Me3S+=O SULFONIUM (20.7) (14.4) (33) (24.5) (30.7) (27.6) i-Pr MeR= SULFIMIDES & SULFOXIMINES X=H Ph SPh (29.0) (29.0) (24.5) (18.2) (27.2) (33) SOPh Ph HX= (35.1) SULFOXIDES (26.3)PhSCH=CHCH2SPh (22.9) (23.6) (24.0) (24.3) t-Bu i-Pr Et MeR= RSCH2CN (19.1) (20.8) (30.7) CN CO2Me Ph X= (30.5) (31.3)(PrS)3CH (22.8)(PhS)3CH (26.7)PhSCHPh2 (23.0)(PhS)2CHPh (23.4)MeSCH2SO2Ph (24.9) (11.0) (20.3) (30.8) (11.8) (16.9) (18.7) (20.8) (30.8) POPh2 SO2CF3 SO2Ph SPh NO2 COPh COCH3 CN PhX= PhSCH2X SULFIDES (30.0) (30.2) (25.2) (26.7) (30.1) (28.2) H2O (DMSO) SubstrateSubstrateSubstrate pKaSubstrate HETERO-AROMATICS NITRILES p。