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pKa's of Inorganic and Oxo-AcidsSubstratepKa H2O (DMSO)INORGANIC ACIDS(32)15.7H3O -1.7H2S7.00HBr-9.00 (0.9)HCl-8.03.17HOCl7.5H2O HX NC6H44.76 (12.3)1.682.662.862.863.121.290.65-0.253.773.6, 10.34.2 (11.1)2.17HSCN4.00H2SO31.9, 7.21m-O2NC6H42.45H2SO4-3.0, .99HNO32.12, 7.21,12.32-1.3HNO23.29H2CrO4-0.98, 6.50o-(CH3)3N C6H4 1.37p-(CH3)3N C6H4 .24B(OH)3HOOHH3PO4SubstrateCARBOXYLIC ACIDSH2OHFpKaSubstrate4.47pKa H2O 8.4p-O2NC6H4OH7.110.22-naptholPh OH-7.8OHPhCH3PhO Ph(10.8)(19.1)Me11.6cis-CO2H1.92, 6.23MeO HH-2.05O -2.2 HOHOH11.3 (20.1)-1.8SMeMePhOHNO HOHNN OH8.88 (13.7)(NH)(18.5)0.79( 1.63)MeNMeOH( 5.55)MeMeSULFINIC & SULFONIC ACIDSO9.23-3.8O MeOH4.253.02, 4.38-6.5MeH(17.1)PEROXIDESR Htrans-CO2H-6.2HOPh-12.4OHOHOXIMES & HYDROXAMIC ACIDSNN m-O2NC6H4OHp-OMeC6H4OHpKa H2O (DMSO)PROTONATED SPECIESHOHORChem 206MeOOH11.5CH3CO3H8.2MeOSOH-2.6OPhS2.1OH*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: x.htmpKa Table.1 11/4/05 1:43 PM

D.H. Ripin, D.A. EvanspKa H2OSubstrate(DMSO) SubstratepKaPROTONATED NITROGENN H49.2EtN H10.63i-Pr2N H2Et3N HPhN H3PhN (Me)(10.5)11.0510.75 (9.00)2H4.6(3.6)5.20(2.50)Ph2N H20.782-napthal-N H34.16H2NN H38.12HON H3H2O (DMSO)Quinuclidine11.0MeMeH2NN(26.5)AMIDES & CARBAMATES(9.80)R H(23.5)CH3 15.1 (25.5)NH2Ph(23.3)CF3(17.2)(urea) NH2(26.9)OEt(24.8)N H2 8.36ON-Me morpholineR7.38NO2 O2NNH3-9.3NO2OEtN HDABCOO2.97, 8.82(2.97, 8.93)N NH6.90, 9.95 NH3 NH3Proton SpongePhCN H NH3-9.0, 12.0(--, 7.50)(21.6)OOAc2NH8.30ONH( RDAZONES,- IDES, & -INESN H2Me2N(13.6)NMe2OPhNNH2PhDBU(26.1)(12) (estimate)NH NHNH9.2NHHNR H (PPTS)t-BuMeCl, H6.95O NN(19.8)N(13.9)X O (24.4)X S (27.0)SH(29.4)MeNMe5.21 (3.4)(0.90)H4.95ONHNHN(12.1)N (18.4)(4.46)6.75HMeR-100.72*Values 0 for H2O and DMSO, and values 14 for water and 35 for DMSO were extrapolated using various methods.(15)NHNHH NH(18.6)XSDMAPMe2NNHNN (23.0)NHX O (14.8)X S (11.8)(17.2)PROTONATED HETEROCYCLES(16.4)N(11.9)X O (24)X X S 6)NHNH2RO(17.3)(15.0)R MePhHETEROCYCLES(17.5)R MePh(16.1)CF3 6.3 (9.7)MeSO2NHPh(12.9)RSO2NH2On 1 (24.1)n 2 (26.4)(14.7)8.88 (13.7)(NH)OHSULFONAMIDENBnONHONHOHH3N 12 (20.5)PhONHpKa H2O (DMSO)SubstrateHYDROXAMIC ACID & AMIDINESIMIDESHN34.7 (7.9)NH3(41)38i-Pr2NH(36 THF))26(THF) (30)TMS2NHPhNH2 (30.6)MePh2NH (25.0)MeNCNH2 (16.9)NH (37)NH (44)OMorpholinepKa H2O (DMSO)SubstrateAMINES5.96HN Chem 206pKa's of Nitrogen AcidsN MeMe(16.5)i-PrNHMeFor a comprehensive compilation of Bordwell pKa data see: x.htmpKa Table.2 11/4/05 1:43 PMN i-Pr(24)

D.H. Ripin, D.A. EvanspKa H2O (DMSO)SubstratepKa H2O (DMSO)SubstrateHYDROCARBONSO53(Me)2CH251CH2 CH250CH44846(56)43(44)t-BuOOMeOPhH41Ph2CH233.5 (32.2)(43)31.5 (30.6)24(28.8)23PhCCHXC6H4CH3X p-CN(30.8)p-NO2(20.4)O13SMeO(15.7)(20.1)H2EtOi-PrO i-Pr(20.9)(26.6)PhMe2NOSPhON Me3(25.9)(24.9)OCNNO(18.2)(18.0)Me2N(17.2)MeS 36(25.7)Me2NX 19-20 (27.1)O(28.3)nMen i-PrOPhOX(26.3)[30.2 (THF)]PhLiOt-Bu N20X 26.1)Me(20.0)AMIDESp-COPhMeN Me3MeOPhCH3HCCH(23.6)EtO43Ph3CHPhOOOMeOEtOpKa H2O (DMSO)SubstrateKETONES24.5 (30.3)t-BuOpKa H2O (DMSO)SubstrateESTERS(Me)3CHCH2 CHCH3Chem 206pKa's of CH bonds in Hydrocarbons and Carbonyl CompoundsXX HCH3PhCOCH3COPhCNFOMeOPhSPhSePhNPh2N (32.4)MeMeMe*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: x.htmpKa Table.3 11/4/05 1:44 PM

pKa's of CH bonds at Nitrile, Heteroaromatic, and Sulfur Substituted CarbonD.H. Ripin, D.A. EvanspKa H2O (DMSO)SubstrateNITRILESNCX )N XX S OPhS (18.2)(16.3)CH2PhSULFIMIDES & SULFOXIMINESPhPhCO2MeCNRSCH2CNR 2.9)PhSCH CHCH2SPh(26.3)BuSH10-11 (17.0)(10.3)PhSH 7SPhOPhOPhOPhX HCH3t-BuPhCH CH2CH CHPhCCHCCPhCOPhCOMeOPhN 0.7)Me(24.5)CF3O(33)CF3OMeNMeMeN Si-PrO(26.6)SO(20.7)OS(32.8)Et(PhSO2)2CH2Me*Values 0 for H2O and DMSO, and values 14 for water and 35 for DMSO were extrapolated using various methods.pKa Table.4 11/4/05 1:44 .2)(20.2)OSNTsSXORR Mei-PrOOSPhNTsXX XMeSNSX 9)SSubstrate pKa H2O (DMSO)SULFOXIDESPhSCH2XX SpKa H2O (DMSO)SubstrateSULFIDESXHCH3PhCOPhCONR2CO2EtCNOPhN Me3SPhSO2PhpKa H2O (DMSO)SubstrateChem 206(14.3)

D. H. Ripin, D. A. EvanspKa's of CH bonds at Heteroatom Substituted Carbon & ReferencespKa H2O SO2Ph(27.9)PhOCH2CN(28.1)O(22.85)PhNITROP H4-14RNO2MeP H32.7Et3P HPh3P CH3Ph3P i-PrPh3P CH2COPh9.1(22.4)(21.2)(6.2)R CH3CH2MeCHMe2CH2PhCH2BnPh3P CH2CN(7.0)PHOSPONATES &PHOSPHINE 1.3)PhSeCH2Ph(31.0)PhSeCH CHCH2SePh(27.2)X OPh2PAMMONIUMX Me3N CH2XX 16.4)ClSiMe3n )Ph2PCH2SO2Ph(20.2)PhJACS 97, 7007 (1975)JACS 97, 7160 (1975)JACS 97, 442 (1975)JACS 105, 6188 (1983)JOC 41, 1883 (1976)JOC 41, 1885 (1976)JOC 41, 2786 (1976)JOC 41, 2508 (1976)JOC 42, 1817 (1977)JOC 42, 321 (1977)JOC 42, 326 (1977)JOC 43, 3113 (1978)JOC 43, 3095 (1978)JOC 43, 1764 (1978)JOC 45, 3325 (1980)JOC 45, 3305 (1980)JOC 45, 3884 (1980)JOC 46, 4327 (1981)JOC 46, 632 (1981)JOC 47, 3224 (1982)JOC 47, 2504 (1982)Acc. Chem. Res. 21, 456 (1988)Unpublished results of F. BordwellWater:IMINES(20.6)(19.4)(14.6) SepKa H2O (DMSO)SubstratePHOSPHONIUM(49)MeOpKa H2O (DMSO)SubstrateChem 206(24.3)PhOxime ethers are 10 pka units lessacidic than their ketone counterpartsStreitwieser, JOC 1991, 56, 1989Advanced Org. Chem., 3rd Ed.J. March (1985)Unpublished results of W. P. JencksTHF:JACS 110, 5705 (1988)See cited website below for additionaldata*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 Brodwell pKa data see: x.htmpKa Table.5 11/4/05 1:45 PM

DMSO Acidities of Common HeterocyclesBordwell, ACR, 1988, 21, 456Bordwell SSHHNHSNHNHNMeSMeN MeMeNNHN HMeN MeMe13.3Pka Table.6.cdx 11/4/05 1:45 PM14.811.829.416.518.4Me24Me