D.H. Ripin, D.A. Evans pKa's of Inorganic and Oxo-Acids Chem 206
D.H. Ripin, D.A. Evans pKa's of Inorganic and Oxo-Acids Chem 206
D.H. Ripin, D.A. Evans pKa's of Inorganic and Oxo-Acids Chem 206
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D.H. <strong>Ripin</strong>, D.A. <strong>Evans</strong><br />
<strong>pKa's</strong> <strong>of</strong> CH bonds at Nitrile, Heteroaromatic, <strong>and</strong> Sulfur Substituted Carbon<br />
<strong>Chem</strong> <strong>206</strong><br />
Substrate pKa H 2 O (DMSO) Substrate pKa H 2 O (DMSO) Substrate pKa H 2 O (DMSO) Substrate pKa H 2 O (DMSO)<br />
NC<br />
X= H<br />
CH 3<br />
Ph<br />
COPh<br />
CONR 2<br />
CO 2 Et<br />
CN<br />
OPh<br />
N + Me 3<br />
SPh<br />
SO 2 Ph<br />
N<br />
N<br />
N<br />
N +<br />
O -<br />
O<br />
S<br />
X<br />
NITRILES<br />
11<br />
HETERO-AROMATICS<br />
Ph<br />
Ph<br />
Ph<br />
Ph<br />
Ph<br />
Ph<br />
(31.3)<br />
(32.5)<br />
(21.9)<br />
(10.2)<br />
(17.1)<br />
(13.1)<br />
(11.1)<br />
(28.1)<br />
(20.6)<br />
(20.8)<br />
(12.0)<br />
(28.2)<br />
(30.1)<br />
(26.7)<br />
(25.2)<br />
(30.2)<br />
(30.0)<br />
PhSCH 2 X<br />
X= Ph<br />
CN<br />
COCH 3<br />
COPh<br />
NO 2<br />
SPh<br />
SO 2 Ph<br />
SO 2 CF 3<br />
POPh 2<br />
MeSCH 2 SO 2 Ph<br />
PhSCHPh 2 (26.7)<br />
(PhS) 3 CH<br />
(22.8)<br />
(PrS) 3 CH<br />
(31.3)<br />
Me<br />
S<br />
(30.5)<br />
S S H<br />
(PhS) 2 CHPh<br />
(23.0)<br />
X=<br />
S<br />
S<br />
X<br />
Ph<br />
CO 2 Me<br />
CN<br />
RSCH 2 CN<br />
R=<br />
Me<br />
Et<br />
i-Pr<br />
t-Bu<br />
SULFIDES<br />
(30.8)<br />
(20.8)<br />
(18.7)<br />
(16.9)<br />
(11.8)<br />
(30.8)<br />
(20.3)<br />
(11.0)<br />
(24.9)<br />
(23.4)<br />
(30.7)<br />
(20.8)<br />
(19.1)<br />
(24.3)<br />
(24.0)<br />
(23.6)<br />
(22.9)<br />
PhSCH=CHCH 2 SPh (26.3)<br />
BuSH<br />
10-11 (17.0)<br />
PhSH<br />
≈7 (10.3)<br />
X= H (35.1)<br />
Ph<br />
(29.0)<br />
SPh (29.0)<br />
H<br />
Ph<br />
SOPh<br />
Me 3 S + =O<br />
SULFONIUM<br />
(33)<br />
(27.2)<br />
(18.2)<br />
*Values 14 for water <strong>and</strong> >35 for DMSO were extrapolated using various methods.<br />
Me<br />
Ph S X<br />
X=<br />
Ph<br />
Ph<br />
O<br />
S<br />
O<br />
O<br />
S<br />
CHPh 2<br />
SULFOXIDES<br />
X<br />
(24.5)<br />
(18.2)<br />
(16.3)<br />
SULFIMIDES & SULFOXIMINES<br />
NTs<br />
S<br />
Ph R<br />
Ph S Me<br />
R= Me<br />
i-Pr<br />
O NTs<br />
O NMe<br />
S<br />
Ph Me<br />
O N + Me 2<br />
Ph S Me<br />
O NTs<br />
Ph<br />
Me<br />
S+ CH 2 Ph<br />
S<br />
CH 2 Cl<br />
(27.6)<br />
(30.7)<br />
(24.5)<br />
(33)<br />
(14.4)<br />
(20.7)<br />
Ph<br />
O<br />
S<br />
O<br />
SULFONES<br />
X<br />
X= H<br />
(29.0)<br />
CH 3<br />
(31.0)<br />
t-Bu<br />
(31.2)<br />
Ph<br />
(23.4)<br />
CH=CH 2<br />
(22.5)<br />
CH=CHPh<br />
(20.2)<br />
CCH<br />
(22.1)<br />
CCPh<br />
(17.8)<br />
COPh<br />
(11.4)<br />
COMe<br />
(12.5)<br />
OPh<br />
(27.9)<br />
N + Me 3<br />
(19.4)<br />
CN<br />
(12.0)<br />
NO 2<br />
(7.1)<br />
SMe<br />
(23.5)<br />
SPh<br />
(20.5)<br />
SO 2 Ph<br />
(12.2)<br />
PPh 2 (20.2)<br />
O<br />
O<br />
Ph S CHPh 2<br />
O O<br />
S<br />
Me<br />
O<br />
Me<br />
O<br />
S<br />
CF 3 Me<br />
O O<br />
S<br />
CF 3 i-Pr<br />
O O<br />
CF 3<br />
Et<br />
O<br />
S<br />
S<br />
O<br />
Et<br />
(PhSO 2 ) 2 CH 2 Me<br />
(22.3)<br />
(31.1)<br />
(18.8)<br />
(21.8)<br />
(26.6)<br />
(32.8)<br />
(14.3)
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