pKa_数据表

D.H. Ripin, D.A. Evans *Values <0 for H2O and DMSO, and values >14 for water and >35 for DMSO were extrapolated using various methods. 0.79 SULFINIC & SULFONIC ACIDS PEROXIDES H2OpKa (DMSO)(DMSO)pKa H2OH2OpKa (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 11.6HOOH -3.0, 1.99H2SO4 1.9, 7.21H2SO3 4.00HSCN 2.12, 7.21, 12.32 H3PO4 7.00H2S -1.7 15.7 H3O+ H2O -1.3HNO3 3.29HNO2 4.72HN3 9.24NH4Cl 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 CH3 4.76 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+C6H4 3.43 4.47 C6H5 4.25 3.02, 4.38 Substrate Substrate (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) pKa H2O 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 Ph CH3 OH O+ H H Me S OH O O Ph S OH O S OH MeMe O+ H MePh D.H. Ripin, D.A. Evans *Values <0 for H2O and DMSO, and 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 SubstrateSubstrate Substrate 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 ( ppt 关于艾滋病ppt课件精益管理ppt下载地图下载ppt可编辑假如ppt教学课件下载triz基础知识ppt S) 5.21 (3.4) + DMAP 9.2 + 4.95 (0.90) PhN+(Me)2H 5.20 (2.50) R= t-Bu Me 6.75 (4.46) + 6.95 N-Me morpholine 7.38 Morpholine 8.36 2.97, 8.82 (2.97, 8.93) (9.00) 6.90, 9.95 Quinuclidine 11.0 (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 NITROGEN AMINES PhSO2NH2 MeSO2NH2 CF3SO2NH2 (17.5) (16.1) 6.3 (9.7) HN3 4.7 (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)H2O H2O (DMSO)pKa pKa (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 NNH H2N N N N NH R NH2 O NH O N H Et Ph N H O NH O NH O O O O NH O N H Ph OH Ph Me2N NMe2 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 <0 for H2O and DMSO, and values >14 for water and >35 for DMSO were extrapolated using various methods. HCCH H2O (DMSO)SubstrateSubstrate Substrate pKa Substrate AMIDES HYDROCARBONS pKa (DMSO)H2O H2O (DMSO)pKa pKa (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 PhCCH 23 (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 MeMe Me O X O EtEt S i-Pr i-Pr O O Met-Bu Ph X Ph i-Pr O O LiO O Ph Me O X O O O O O MeMe t-BuO O Met-BuO O Ph EtO O N+Me3 O EtO Me O O OMeMeO O O MeO S N+Me3 O Et2N Ph O Me2N Me2N O SPh N O CN Me2N Me S O MeMe2N O Chem 206 D.H. Ripin, D.A. Evans 11 (10.3) (17.0) ≈7 10-11 PhSH BuSH *Values <0 for H2O and DMSO, and 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 PhX= (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)SubstrateSubstrate Substrate pKa Substrate HETERO-AROMATICS NITRILES pKa (DMSO)H2O H2O (DMSO)pKa pKa (DMSO)H2O 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) SULFONES X= H CH3 t-Bu Ph CH=CH2 CH=CHPh CCH COPh CCPh COMe OPh N+Me3 CN NO2 SMe SPh SO2Ph PPh2 (29.0) (31.0)(31.2) (23.4) (22.5)(20.2) (22.1) (17.8) (11.4) (12.5) (27.9) (19.4)(12.0) (7.1)(23.5) (20.5) (12.2) (20.2) (22.3) (PhSO2)2CH2Me (31.1) (18.8) (21.8) (32.8) (14.3) (26.6) pKa's of CH bonds at Nitrile, Heteroaromatic, and Sulfur Substituted Carbon NC X N Ph PhN N Ph Ph N+ O Ph Ph S O- S O O Ph X S O Ph S CHPh2 OO O Me Me S S SH S S Ph S X O S O X S O CHPh2Ph X Me S NTs Ph S RPh Me NTsO S O NMe MePh Ph S Me N+Me2O S O NTs CH2ClPh Ph S+ CH2Ph Me Me CF3 S Me OO S O O i-PrCF3 Et S Et OO CF3 S OO Chem 206 (24.3) IMINES n (15.8) (17.9) (16.0) (17.8) (26.9) 7 6 5 4 3n= (7.7) (7.1) (11.8) (16.2) (12.2) (16.9) (16.7) (17.2) CH2COPh CH2SO2Ph CH2SPh CH2Bn CH2Ph CHMe2 CH2Me CH3R= RNO2 NITRO (20.3) (29.9) Ph2PCH2SO2Ph Ph2PCH2PPh2 (16.9)CN (24.9)SPhX= PHOSPHINES (28.8) (26.2) (18.6) (16.4) (27.6) SiMe3 Cl CO2Et CN PhX= PHOSPONATES & PHOSPHINE OXIDES (7.0) (6.2) (21.2) (22.4) Ph3P+CH2CN Ph3P+CH2COPh Ph3P+i-Pr Ph3P+CH3 9.1Et3P+H 2.7MeP+H3 -14P+H4 PHOSPHONIUM (24.9) (20.6) (14.6) (19.4) (20.6) CONEt2 CO2Et COPh SO2Ph CNX= Me3N+CH2X AMMONIUM (21.1) (27.9)PhOCH2SO2Ph (28.1)PhOCH2CN (30.7)MeOCH2SO2Ph (49)CH3OPh SELENIDES ETHERS (27.2)PhSeCH=CHCH2SePh (31.0)PhSeCH2Ph (31.3)(PhSe)2CH2 (27.5)PhSeCHPh2 (18.6) H2O (DMSO) D. H. Ripin, D. A. Evans SubstrateSubstrate Substrate pKapKa (DMSO)H2O H2O (DMSO)pKa pKa's of CH bonds at Heteroatom Substituted Carbon & References REFERENCES DMSO: JACS 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. Bordwell Water: Advanced Org. Chem., 3rd Ed. J. March (1985) Unpublished results of W. P. Jencks THF: JACS 110, 5705 (1988) ≈10 *Values <0 for H2O and DMSO, and values >14 for water and >35 for DMSO were extrapolated using various methods. (EtO)2P X O Ph2P O X O2N Ph Ph N Ph PhSe Ph O O Ph MeO Chem 206 Oxime ethers are ~ 10 pka units less acidic than their ketone counterparts Streitwieser, JOC 1991, 56, 1989