D. H. Ripin, D. A.

Evans pKa's of CH bonds at Heteroatom Substituted Carbon & References Chem 206

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PhSeCH=CHCH2SePh (27.2) SiMe3 (28.8) (15.8) Unpublished results of F. Bordwell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(24.3) Unpublished results of W. P. Jencks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.

For a comprehensive compilation of Brodwell pKa data see: http://www.chem.wisc.edu/areas/reich/pkatable/index.htm

pKa Table.5 11/4/05 1:45 PM