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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

pKa Data Compiled by R. Williamspage-1pKa e25Carboxylic acids4, 8Pyrazine26Aliphatic4, 8Aromatic7, 8Quinoline27Phenols9Quinazoline27Alcohols and oxygen acids10, 11Quinoxaline27Amino Acids12Special Nitrogen Compounds28Peptides13Hydroxylamines28Nitrogen Compounds14Hydrazines28Aliphatic amines15, 17, s17, 18, 20Thiols29Nucleosides21Carbon Acids30,31Special Table For complex chelating agents, see also reference 77.Note. This document was compiled by W.P. Jencks and has been added to by F.H. Westheimer

pKa Data Compiled by R. WilliamsACIDSCompoundpKRef.AgOHAl(OH)3As(OH)3H3 AsO 4H2 AsO 4 –HAsO 4 *As 2 O 3H3 AsO 3H3 BO 3H2 B4 O 7HB4 O 7Be(OH) 2HBrHOBrHOClHClO2HClO3HClO4 (70%)CH3 SO 3 HHCNH2 CO 3HCO 3H2 CrO4HCrO4HOCNHZH2 GeO3Ge(OH)4HIHOIHIO3H4 IO6 –H5 IO6HMnO4NH3 OH*NH4 *HN3HNO2HNO3N2 H5 H2 N2 O 2H2 N2 O 2 –H2 OsO 5H2 OH3 O Pb(OH)23.9611.29.222.22, 7.0, 13.06.98*11.53*09.22*9.23*4.009.003.7-9.008.77.53, 7.462.0-1.00-10.00-0.69.406.37, 6.35*, 3.5810.33*-0.986.50*3.923.17*, 0.59*8.59, 12.728.68, 12.7-10.011.00.86.001.64, 1.55, 5.7-1.76.48 (10.92)4282828777742834344312828, 33282831313434, 32302, 30347734, 78283128283434, 28307777282877343434nonenone4 (78)page-2H3 PO 2H2 PO 4 –HPO 4H3 PO 3H2 PO 3 –H4 P 2 O 7H3 P 2 O 7 –H2 P 2 O 7 HP2 O 7 HReO4HSCNH2 SeO3HSeO3H2 SeO4HSeO4H3 SiO 3H2 SO 3H2 SO 4HSO 3HSO 4 –H2 S2 O 4H2 SeHSe–H2 SHS–HSbO 2HTeH2 TeH2 TeO 3Te(OH) 6H2 VO 4 –HVO4 H2 CrO4HOCNHSCNH3 PO 2H3 PO 4H2 S2 O 3H3 AuO3H3 GaO 3H5 IO6H4 V6 O 17H2 NSO 3 H2.0, .002.6, 8.3, 2.62*8.32Strong, 2.02.0010.01.9, 7.0, 1.76*-3.0, , 11.02.7, 8.06.2, 8.88.9514.40.743.730.851.072.12*0.60*, 1.72*13.3, 16.010.32, 11.73.29, 6.70, 15.0(see above!)1.961.0* Indicates a thermodynamic value.2877772877777777773034287728343428, 772877772977777777343434, 78282830307777777777777878787880

PHOSPHATES AND PHOSPHONATESPhosphatesCompoundpKPhosphate1.97, 6.82, 12.5Glyceric acid 2-phosphate 3.6, 7.1Enolpyruvic acid3.5, 6.4Methyl1.54, 6.31Ethyl1.60, 6.62n-Propyl1.88,6.67n-Butyl1.80, se-30.84, 5.67Glucose-40.84, 5.67α-glycero1.40, 6.44β-glycero1.37, 6.343-phosphoglyceric acid1.42, 3.422-phosphoglyceric acid1.42, 3.55, 7.1peroxymonophosphoric acid 4.05diphosphoglyceric acid7.40, 7.99glyceraldehyde2.10, 6.75dioxyacetone1.77,6.45hexose di1.52, 6.31fructose-60.97, 6.11glucose-60.94, 6.11glucose-11.10, 6.13adenylic acid3.8?, 6.2?inosinic acid2.4?, 6.4?ADP2 strong, 6.6ATP3 strong, 6.6pyrophosphoric acid0.9, 2.0, 6.6, 9.4phosphopyruvic acid3.5, 6.38creatine phosphate2.7, 4.5arginine phosphate2.8, 4.5, 9.6, 11.2arginine2.02, 9.0, 12.5amino phosphate(-0.9), 2.8, honatesH 2O3P(CH 2) 4PO3H 2 2, 2.75, 7.54, 8.3857H 2O3P(CH 2) 3PO3H 2 2, 2.65, 7.34, 8.3557H 2O3PCH 2CH(CH 3)PO 3H 2 2, 2.6, 7.00, 9.27 57H 2O3PCH 2PO3H 2 2, 2.57, 6.87, pyl2.55, 7.7557n-butyl2.59, 8.1957isobutyl2.70, 8.4357s-butyl2.74, 8.4857t-butyl2.79, 8.8857neopentyl2.84, 8.65571,1 Dimethylpropyl2.88, 8.9657n-hexyl2.6, 7.957n-dodecyl--, 8.2557CH 3(CH 2) 5CH(COOH)- 1, -57CF 3CCl 3NH 3 CH 2( –OOCCH 2) 2NH CH 2–CHCl 2CH 2CICH 2Br( –OOCCH 22NH (CH 2) 2CH 2INH 3 CH 2CH 2C6H 5CH CHHOCH 2C6H 5NH 2 (CH 2) 3C6H 5NH(CH 2) 3Br(CH 2) 2CH 3(CH 2) 5CH(COO–)C6H 5CH 2NH 3 (CH 2) 4)NH 3 (CH 2) 5NH 3 (CH 2) 10–OOC(CH2) 10(CH 3) 3SiCH 2C6H 5CH 2(C 6H 5)SC-1.16, 3.931.63, 4.812.35, 5.9--, 5.571.14, 5.611.40, 6.301.14, 6.52--, 6.541.30, 6.722.45, 7.002.00, 7.11.91, 7.152.1, ---, 7.172.25, 7.3--, 7.52.3, 7.552.55, 7.552.6, 7.6--, 8.00--, 8.253.22, 8.703.3, 8.43.85, 57Arylphosphonic acids2X-RC6H 3PO3H 2XRCl4-O 2NBr5-O 2NCl5-ClClHBrHBr5-CH 3Cl4-NH 2CH 3O4-O 2NCH 3OHCH 3O4-O 2NHO4-O 2NO2NHFHIHNH 2H--, 7.29CH 3H2.10, 7.68C6H 5HHOOCH1.12, 6.14(a), 6.14(a), 6.631.63, 6.981.64, 7.001.81, 7.15--, 7.331.53, 6.962.16, 7.77--, 8.221.22, 5.391.45, 6.741.64, 6.801.74, 7.065757(a), 8.131.71, 9.1757575757575757575757575757575757**These values were obtained in 50% ethanol.(a) The compounds were not sufficiently soluble.For graphical plots of a large number of substitutedphosphorus compounds see 83.triphosphatetetrametaphosphate8.90, 6.26, 2.302.747777

fluorophosphate0.55, 4.856Phosphonates (Ref. 2)X-H-H-NH 3 -NH 3 X(CH 2)PO 3H 22.357.11.855.35X(CH 2) 2PO3H 22.457.852.457.00X(CH 2) 4PO3H 22.557.55X(CH 2) 5PO3 H22.67.65X(CH 2) 6PO2H 22.67.9X(CH 2) 10PO2H 28.00Phosphines in acetonitrile, see ref. 89.CARBOXYLIC c2.61, 7.85 (enol)Aconitic, trans2.80, 4.46Betaine1.84Citric3.09, 4.75, 5.41Crotonic4.69Dihydroxyfumaric 1.14Dethylenediamine- 2.00, 2.67tetraacetic6.16, 10.26Formic3.77*Fumaric3.03, istic4.40α-keto-β-methyl valeric 2.3Lactic3.86Maleic1.93, 6.58Malic3.40, 5.2Oxaloacetic (trans-enol) 2.56 (cis-enol)2.15, 4.06Protocatechuic4.48Pyruvic2.50Tartaric 2.99, 4.40 or 2.89, 4.40meso3.22, cetic acids, substitutedH4.76*O2N1.68* (CH 3)3N 1.83* (CH 3)2NH 1.95* CH 3NH2 2.16*NH3 2.31*CH 3SO22.36*NC2.43*C 6H5SO22.44HO2C2.83*C 0.65F30.23 (-0.26) (2)HONC43.01F3C3.07*N33.03I3.12C 6H5O3.12C 2H5O2C3.35C 6H5S3.52*CH 3O3.53NCS3.58CH 3CO3.58*C 2H5O3.60n-C 3H7O3.65n-C 4H9O3.66sec.-C4H9O3.67HS3.67*i-C3H7O3.69*CH 3S3.72*i-C3H7S3.72*C 6H5CH 2S3.73*C 2H5S3.74*n-C 3H7S3.77*n-C 4H9S3.81*HO3.83*–O3S4.05(C 6H5)3CS4.30*C 6H54.31*CH 2-CH4.35** Indicates thermodynamic 0202020202020202020202020202020202020202020202020

Unsaturated acids (25 )Compoundtrans-CH 3-CH CHCO 2Hcis-CH3-CH CHCO 2H