Evans pka tables PDF

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Evans pKa tables...

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Chem 206

pKa's of Inorganic and Oxo-Acids Substrate

pKa H2O (DMSO)

H2O

15.7

H3O+

-1.7

H2S

pKa

Substrate

H2O (DMSO)

Substrate

(32)

O X

OH

X= CH3

7.00

HBr

-9.00 (0.9)

HCl

-8.0

(1.8)

HF

3.17

(15)

HOCl

7.5

4.76 (12.3)

(12.9)

HN3

4.72

(7.9)

HO C6H5 o -O2NC6H4

H2SO3

1.9, 7.21

H2SO4

-3.0, 1.99

H3PO4 HNO3

2.12, 7.21, 12.32 -1.3

HNO2

3.29

Ph

16.5

(27.9) (29.3)

17.0

(29.4)

Ph

3.6, 10.3 4.2 (11.1) 2.17

9.4

4.00

15.5

(CF3)2CHOH

-10

HSCN

MeOH i-PrOH

3.12 1.29 0.65 -0.25 3.77

HCN

m-O2NC6H4 p-O2NC6H4

2.45

o -ClC6H4

2.94

m-ClC6H4

3.83

p-ClC6H4

3.99

CF3CH2OH

12.5

(23.5)

9.3

(18.2)

9.95

(18.0)

m-O2NC6H4OH

8.4

p -O2NC6H4OH

7.1

p-OMeC6H4OH

H2CrO4

-0.98, 6.50

CH3SO3H

-2.6

(1.6)

p-OMeC6H4

CF3SO3H

-14

(0.3)

NH4Cl

9.24

B(OH)3

9.23

HOOH

11.6

4.47

Ph

OH OH

Ph

CH3

Ph

-6.2

H O+

Ph

O+

Me

(19.1)

-6.5 Me

-3.8 Me

O+ H

(17.1)

-2.05

H O+ Me

-2.2

H

+

OH

OH

11.3 (20.1)

-1.8

S

Me

Me

Ph O

Ph

-7.8

H

(10.8)

OXIMES & HYDROXAMIC ACIDS

N O H N

OH

8.88 (13.7) (NH)

OH

(18.5)

N+ OH

0.79

(+1.63)

Me Me

N

OH

(+5.55)

Me

Me

SULFINIC & SULFONIC ACIDS

O R

10.2

2-napthol

N

OH

OH

24.0

C6H5OH

-12.4

N+ +

+

c-hex3COH

3.44

o -(CH3)3N+C6H4 1.37 p-(CH3)3N+C6H4 3.43

O

(31.2)

t-BuOH

pKa H2O (DMSO)

PROTONATED SPECIES

15.7

1.68 2.66 2.86 2.86

HClO4

Substrate

HOH

CH2NO2 CH2F CH2Cl CH2Br CH2I CHCl2 CCl3 CF3 H

pKa H2O (DMSO)

ALCOHOLS

CARBOXYLIC ACIDS

INORGANIC ACIDS

PEROXIDES O O

OH

R= H

trans -CO2H cis-CO2H

4.25 3.02, 4.38 1.92, 6.23

MeOOH

11.5

CH3CO3H

8.2

Me

S

OH

-2.6

O Ph

S

2.1 OH

*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

pKa Table.1 11/4/05 1:43 PM

D.H. Ripin, D.A. Evans pKa

Substrate

H2O

(DMSO) Substrate

4 EtN+H

9.2

(10.5)

10.6

3

i-Pr2N+H2

11.05

Et3N+H

10.75 (9.00)

PhN+H3

4.6

(3.6)

PhN (Me)2H

5.20

(2.50)

Ph2N+H2

0.78

2-napthal-N+H3

4.16

H2NN+H3

8.12

+

HON+H

H2O (DMSO)

pKa

PROTONATED NITROGEN N+ H

N+ H

11.0

HN3 NH3 i -Pr2NH TMS2NH PhNH2 (30.6)

Ac2NH Me Me

NH

(44)

H2N

Me Me N

(26.5)

AMIDES & CARBAMATES

(9.80)

N+H2

O

N-Me morpholine

8.36

R

(23.5) R= H CH3 15.1 (25.5) Ph (23.3) (17.2) CF3

NH2

7.38

NO2 +

O2 N

NH3

-9.3

NO2

2.97, 8.82 (2.97, 8.93)

N+

6.90, 9.95

+NH 3

+NH

3

Proton Sponge PhCN+H

OEt

(24.8)

+NH

3

-9.0, 12.0 (--, 7.50)

12 (20.5)

Ph

(21.6)

O

O

( )n O

(20.8) O

NH

R

NH2

8.88 (13.7) (NH)

H N

H N

GUANIDINIUM, HYRDAZONES,- IDES, & -INES N+H2 (13.6) NNH2 (21.6) Me2N

NMe2 O

Ph

Ph

DBU

(12) (estimate) +

R

X= O (14.8) X= S (11.8) N H

N H

9.2

NH HN

R= H (PPTS) t-Bu Me Cl, H

6.95

NH

N

N

(19.8)

N

(13.9)

N

H

X= O (24.4) X= S (27.0)

S H

+

NH

(18.6)

X

S

DMAP Me2N

HN

N

N H +

N

X= O (24) S (13.3)

(26.1)

PROTONATED HETEROCYCLES

(23.0)

NH

X X=

(17.2)

PhSO2NHNH2 PhNHNHPh

(16.4)

N

(11.9) N

N H X

NHNH2

H N

N

Me

(18.9)

(20.95)

H

(29.4) Me

5.21 (3.4) NMe O + H 4.95 (0.90) NH O NH N N + (18.4) (12.1) 6.75 (4.46) H Me R -10 0.72 *Values 14 for water and >35 for DMSO were extrapolated using various methods. (15)

O

(17.3) (15.0)

R= Me Ph

HETEROCYCLES

(17.5) R = Me (16.1) Ph CF3 6.3 (9.7) (12.9) MeSO2NHPh

O

n= 1 (24.1) n= 2 (26.4)

(17.9)

OH N H NSO2Ph

Ph

RSO2NH2

N

Bn NH

(14.7)

NH

O

NH

O

H H3N+

(26.9) O

N H

Et

N+ H

DABCO

(urea) NH2 O

8.30

O

SULFONAMIDE (37)

NH

O

NH

pKa H2O (DMSO)

Substrate

HYDROXAMIC ACID & AMIDINES

IMIDES O

4.7 (7.9) (41) 38 (36 THF)) 26(THF) (30)

Ph2NH (25.0) NCNH2 (16.9)

O

Morpholine

pKa H2O (DMSO)

Substrate

AMINES

5.96

3

Quinuclidine

Chem 206

pKa's of Nitrogen Acids

N+ Me Me

(16.5) i -Pr

N H

Me

For a comprehensive compilation of Bordwell pKa data see: http://www.chem.wisc.edu/areas/reich/pkatable/index.htm pKa Table.2 11/4/05 1:43 PM

N+

i -Pr

(24)

D.H. Ripin, D.A. Evans

pKa H2O (DMSO)

Substrate

pKa

Substrate

O

53

(Me)2CH2

t-BuO

51

CH2=CH2

50

CH4

48 46 43

O

t-BuO

Me

EtO

(20.0) 11

41

Ph2CH2

33.5 (32.2)

(43)

HCCH

31.5 (30.6) 24

PhCCH

23

(28.8)

XC6H4CH3 X= p-CN

(30.8)

p-NO2

(20.4)

MeO

O

13

(15.7)

OMe

O S

MeO

Me2N

Me

(26.1)

20

(20.1)

Ph

SPh

(18.0)

N+Me3

(24.9)

O CN

N

(17.2)

O

(18.2) Me2N

Me

S

~36

H2

(25.9)

O

O

15

(26.6)

O

Et2N

Me

(25.7) Me2N

O -i Pr

t-Bu O

X

X=

19-20 (27.1)

O

(28.3)

n

Me

n=

(26.3) i -Pr O Ph

O

(26.9)

p-COPh

i-Pr

Ph

AMIDES

Me2N

Et O

[30.2 (THF)]

Ph

LiO

Et

9

(26.5) (19.8) (18.7) (13.3) (12.5)

(27.7) (20.9)

S

O

X= H Ph SPh COCH3 SO2Ph

(14.2)

Me O

Me X

O

EtO

PhCH3

Me

N+Me3

(44)

43

Me

(23.6)

H2O (DMSO)

O

O Me

Ph

O

pKa

Substrate

KETONES

O

(56)

PhH

Ph3CH

pKa H2O (DMSO)

Substrate

24.5 (30.3)

O

CH2=CHCH3

H2O (DMSO)

ESTERS

HYDROCARBONS (Me)3CH

Chem 206

pKa's of CH bonds in Hydrocarbons and Carbonyl Compounds

X

X= H CH3 Ph COCH3 COPh CN F OMe OPh SPh SePh NPh2 N+Me3 NO2 SO2Ph

(24.7) (24.4) (17.7) (14.2) (13.3) (10.2) (21.6) (22.85) (21.1) (16.9) (18.6) (20.3) (14.6) (7.7) (11.4)

H OMe NMe2 Br CN

(24.7) (25.7) (27.5) (23.8) (22.0)

4 5 6 7 8

(25.1) (25.8) (26.4) (27.7) (27.4)

O

O

O

(28.1)

(29.0)

(25.5)

O

(32.4) Me

Me

Me

*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

pKa Table.3 11/4/05 1:44 PM

D.H. Ripin, D.A. Evans pKa

Substrate

pKa's of CH bonds at Nitrile, Heteroaromatic, and Sulfur Substituted Carbon H2O (DMSO)

X=

X

(31.3)

H CH3 Ph COPh CONR2 CO2Et CN OPh N+Me3 SPh SO2Ph

(32.5) (21.9) (10.2)

11

(17.1) (13.1) (11.1) (28.1) (20.6) (20.8) (12.0)

(30.8) (20.8) (18.7) (16.9) (11.8) (30.8) (20.5) (11.0) (24.9)

MeSCH2SO2Ph

(23.4)

PhSCHPh2

(26.7)

(PhS)3CH

(22.8)

HETERO-AROMATICS

(31.3)

N

(28.2)

Ph

S H

(23.0)

(26.7)

Ph

N+

Ph

(25.2)

O-

(30.2)

Ph O

S

(30.0)

Ph

(33) (27.2) (18.2)

O

(24.5)

S

Ph

CHPh2

SULFONIUM Me3

S+=O

S+

Ph

(18.2) (16.3)

CH2Ph

X

Ph

Ph CO2Me CN RSCH2CN R= Me X=

Et i-Pr t-Bu

S

R

O Ph

Me

(20.8) (19.1)

S

(24.5)

Ph

CF3 O

(33)

CF3 O

(14.4)

CF3

(20.7)

Et

PhSCH=CHCH2SPh (26.3) 10-11 (17.0) BuSH (10.3) ≈7 PhSH

Ph O

NMe S

S

Ph O Ph

S

Me N+Me2 Me NTs CH2Cl

Me O

O

NTs

O

(31.1)

S

(27.6) (30.7)

(24.3) (24.0) (23.6) (22.9)

(22.3)

CHPh2 O O

R= Me i -Pr

Me

S

(18.8) Me O

(21.8)

S

i -Pr O

(26.6)

S

O

O S

(32.8) Et

(PhSO2)2CH2Me

*Values 14 for water and >35 for DMSO were extrapolated using various methods.

pKa Table.4 11/4/05 1:44 PM

(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)

O S

(30.7)

O

X

X= H CH3 t-Bu Ph CH=CH2 CH=CHPh CCH CCPh COPh COMe OPh N+Me3 CN NO2 SMe SPh SO2Ph PPh2

SULFIMIDES & SULFOXIMINES NTs

S N

X

X= H Ph SOPh

O S

Ph

(35.1) (29.0) (29.0)

O

S

Ph

S

(30.1)

X

S

(PhS)2CHPh

Ph

S

Me

Me

(30.5) N

SULFONES O

X= H Ph SPh

Me

S

Substrate pKa H2O (DMSO)

SULFOXIDES O

PhSCH2X X= Ph CN COCH3 COPh NO2 SPh SO2Ph SO2CF3 POPh2

(PrS)3CH

pKa H2O (DMSO)

Substrate

SULFIDES

NITRILES NC

pKa H2O (DMSO)

Substrate

Chem 206

(14.3)

D. H. Ripin, D. A. Evans pKa

Substrate

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

H2O (DMSO)

CH3OPh

(49)

MeOCH2SO2Ph

(30.7)

PhOCH2SO2Ph

(27.9)

PhOCH2CN

(28.1)

O

(22.85) Ph

RNO2

MeP+H3

2.7

Et3P+H Ph3P+CH3 Ph3P+ i-Pr Ph3P+CH2COPh Ph3P+CH2CN

9.1 (22.4) (21.2) (6.2)

R= CH3 CH2Me CHMe2 CH2Ph CH2Bn

(27.5)

(PhSe)2CH2

(31.3)

PhSeCH2Ph

(31.0)

PhSeCH=CHCH2SePh

(27.2)

X=

X= Me3N+CH2X X= CN SO2Ph COPh CO2Et CONEt2

Ph

(27.6)

CN CO2Et

(16.4)

n=

(18.6) (26.2) (28.8)

(20.0) (24.9)

(26.9)

4

(17.8)

5 6

(16.0) (17.9) (15.8)

X

SPh CN

(24.9) (16.9)

N

Ph2PCH2PPh2

(29.9)

Ph2PCH2SO2Ph

(20.2)

Ph

(24.3) Ph

PHOSPHINES

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:

IMINES

(20.6) (19.4) (14.6)

3

7

O

AMMONIUM

(11.8) (7.1) (7.7)

X

Cl SiMe3 Ph2P

(17.2) (16.7) (16.9) (12.2) (16.2)

n

(EtO)2P

REFERENCES DMSO:

O2N

O

(18.6)

≈10

CH2SPh CH2SO2Ph CH2COPh

(7.0)

PHOSPONATES & PHOSPHINE OXIDES

Ph

H2O (DMSO)

NITRO -14

O

PhSeCHPh2

pKa

Substrate

P+H4

SELENIDES

PhSe

H2O (DMSO)

PHOSPHONIUM

ETHERS

MeO

pKa

Substrate

Chem 206

Advanced Org. Chem., 3rd Ed. J. March (1985) Unpublished results of W. P. Jencks

Ph

Oxime ethers are ~ 10 pka units less acidic than their ketone counterparts Streitwieser, JOC 1991, 56, 1989

THF: JACS 110, 5705 (1988) See cited website below for additional data

*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

DMSO Acidities of Common Heterocycles Bordwell, ACR, 1988, 21 , 456 Bordwell http://www.chem.wisc.edu/areas/reich/pkatable/index.htm N

N N H

23.0

O

N H

19.8

18.6

N H

24.0

13.9

20.8

11.9

18.0

O

O N H

N H

N H

16.4

O

N H

N

N

N H

O N H

N

N

N

O

O

N H

15.0

N H

12.1

O

N H

26.4

O

24.0 Me

O

S

S

S

H

H N H

S N H

N H

N

Me

N+ Me

Me

Me N

Me

N

Me

N+

H

H N+ Me

Me Me

13.3

Pka Table.6.cdx 11/4/05 1:45 PM

14.8

11.8

29.4

16.5

18.4

24...