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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
*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
Substrate pKa H2O (DMSO) Substrate pKa H2O (DMSO) Substrate pKa H2O (DMSO) Substrate pKa H2O (DMSO)
*Values <0 for H2O and DMSO, and values >14 for water and >35 for DMSO were extrapolated using various methods.
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 24.5 (30.3)
X
(Me)2CH2 51 t-BuO Me Me X
O (26.5)
X= H
CH2=CH2 Ph (23.6) Ph (19.8) X= H (24.7)
50
t-BuO (18.7) (25.7)
O SPh OMe
CH4 48 (56) NMe2 (27.5)
(20.0) COCH3 9 (13.3)
N+Me3 (23.8)
46 EtO SO2Ph (12.5) Br
O O O CN (22.0)
CH2=CHCH3 43 (44) 11 (14.2) 19-20 (27.1) O
EtO Me Et Et
O
PhH 43 O O
13 (15.7) (28.3) n
PhCH3 (43) i-Pr O i-Pr
41 MeO OMe
O (27.7)
Ph2CH2 33.5 (32.2) t-Bu O Me
n= 4 (25.1)
S (20.9) (25.8)
MeO (26.3) 5
Ph3CH 31.5 (30.6)
S Ph i-Pr 6 (26.4)
HCCH 24 O O 7 (27.7)
Ph
[30.2 (THF)] 8 (27.4)
PhCCH 23 (28.8) X
LiO Ph
XC6H4CH3 X= H (24.7)
AMIDES
CH3 (24.4) (28.1)
X= p-CN (30.8) O O
(26.6) Ph (17.7)
p-NO2 (20.4) Ph COCH3 (14.2)
Me2N
O COPh (13.3) (29.0)
p-COPh (26.9) (25.9) O
SPh CN (10.2)
Me Me Me2N
O F (21.6)
(26.1) (24.9) (22.85) O
N+Me3 OMe (25.5)
Me Me Et2N
O OPh (21.1)
SPh (16.9)
CN
20 (20.1) N (17.2) SePh (18.6)
NPh2 (20.3) O
O O (32.4)
15 (18.0) (18.2) N+Me3 (14.6)
Me2N Me NO2 (7.7) Me Me
S
H2 ~36 (25.7) SO2Ph (11.4)
Me2N Me
*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
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 (30.8) Me Ph
X= H (31.3) CN (20.8) X= H (35.1) (29.0)
Ph (29.0) X= H
CH3 (32.5) COCH3 (18.7) SPh (29.0) CH3 (31.0)
(21.9) COPh (16.9) O t-Bu (31.2)
Ph
(10.2) NO2 (11.8) S X Ph (23.4)
COPh (30.8)
SPh Ph CH=CH2 (22.5)
CONR2 (17.1) SO2Ph (20.5) X= H (33) CH=CHPh (20.2)
CO2Et (13.1) Ph (27.2) (22.1)
SO2CF3 (11.0) (18.2) CCH
POPh2 (24.9) SOPh (17.8)
CN 11 (11.1) O CCPh
COPh (11.4)
OPh (28.1) MeSCH2SO2Ph (23.4) S (24.5)
Ph CHPh2 COMe (12.5)
N+Me3 (20.6) PhSCHPh2 (26.7) OPh (27.9)
SPh (20.8)
(PhS)3CH (22.8) SULFONIUM N+Me3 (19.4)
CN (12.0)
SO2Ph (12.0)
(PrS)3CH (31.3) Me3S+=O (18.2) NO2 (7.1)
Me SMe (23.5)
Me (16.3) (20.5)
HETERO-AROMATICS S SPh
S+
(30.5) Ph CH2Ph SO2Ph (12.2)
S S PPh2 (20.2)
(28.2) H
Ph SULFIMIDES & SULFOXIMINES O O
N (PhS)2CHPh (23.0) S (22.3)
NTs Ph CHPh2
S
(30.1) X S O O
N Ph Ph R (31.1)
S
S R= Me (27.6) Me Me
N X= Ph (30.7) i-Pr (30.7) O O
(26.7) O NTs (18.8)
Ph CO2Me (20.8) S
S (24.5) CF3 Me
CN (19.1) Ph Me O O
RSCH2CN O NMe S (21.8)
Ph (24.3) (33) CF3 i-Pr
N+
(25.2) R= Me S
O O
Ph Me
Et (24.0) N+Me2 S (26.6)
O- O
(23.6) (14.4) CF3
i-Pr S
Ph (30.2) (22.9) Ph Me O O
O
t-Bu O NTs (32.8)
S
PhSCH=CHCH2SPh (26.3) S (20.7) Et Et
Ph (30.0) Ph CH2Cl
S BuSH 10-11 (17.0) (PhSO2)2CH2Me (14.3)
PhSH ≈7 (10.3)
*Values <0 for H2O and DMSO, and values >14 for water and >35 for DMSO were extrapolated using various methods.
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, 7007 (1975)
MeP+H3 2.7 R= CH3 ≈10 (17.2) JACS 97, 7160 (1975)
MeOCH2SO2Ph (30.7)
Et3P+H 9.1 CH2Me (16.7) JACS 97, 442 (1975)
PhOCH2SO2Ph (27.9) JACS 105, 6188 (1983)
Ph3P+CH3 (22.4) CHMe2 (16.9) JOC 41, 1883 (1976)
PhOCH2CN (28.1) Ph3P+i-Pr (21.2) CH2Ph (12.2) JOC 41, 1885 (1976)
O JOC 41, 2786 (1976)
Ph3P+CH2COPh (6.2) CH2Bn (16.2)
MeO (22.85) JOC 41, 2508 (1976)
Ph Ph3P+CH2CN (7.0) CH2SPh (11.8) JOC 42, 1817 (1977)
CH2SO2Ph (7.1) JOC 42, 321 (1977)
CH2COPh (7.7) JOC 42, 326 (1977)
SELENIDES PHOSPONATES & JOC 43, 3113 (1978)
PHOSPHINE OXIDES O2N JOC 43, 3095 (1978)
O O JOC 43, 1764 (1978)
n JOC 45, 3325 (1980)
PhSe (18.6) (EtO)2P X
Ph JOC 45, 3305 (1980)
X= Ph (27.6) (26.9) JOC 45, 3884 (1980)
PhSeCHPh2 (27.5) n= 3 JOC 46, 4327 (1981)
CN (16.4)
(PhSe)2CH2 (31.3) 4 (17.8) JOC 46, 632 (1981)
CO2Et (18.6) JOC 47, 3224 (1982)
5 (16.0)
PhSeCH2Ph (31.0) Cl (26.2) JOC 47, 2504 (1982)
6 (17.9) Acc. Chem. Res. 21, 456 (1988)
PhSeCH=CHCH2SePh (27.2) SiMe3 (28.8) (15.8) Unpublished results of F. Bordwell
O 7
Ph2P X Water:
AMMONIUM IMINES
X= SPh (24.9) Advanced Org. Chem., 3rd Ed.
N Ph J. March (1985)
Me3N+CH2X CN (16.9)
(24.3) Unpublished results of W. P. Jencks
X= CN (20.6) Ph Ph
SO2Ph (19.4) PHOSPHINES Oxime ethers are ~ 10 pka units less THF:
(14.6) acidic than their ketone counterparts JACS 110, 5705 (1988)
COPh
Streitwieser, JOC 1991, 56, 1989
CO2Et (20.0) Ph2PCH2PPh2 (29.9) See cited website below for additional
data
CONEt2 (24.9) Ph2PCH2SO2Ph (20.2)
*Values <0 for H2O and DMSO, and values >14 for water and >35 for DMSO were extrapolated using various methods.
N N N N
N N N
N N N N N N
H H H H H H
O O O
O
O O O
N N N N N O N O
H H H H H H
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
13.3 14.8 11.8 29.4 16.5 18.4 24