37O TABLE

EFFECTSOF STRUCTUREON REACTIVITY 9.4 The o, o+,

on

CHAPTER 9 Groups op
t czb

and o-

Yalues for Some Common om

For the unsubstitutedcase,

Group

oNMe2 NHz OH OMe CMe3 Me H Ph

coo
F CI Br I
N:NPh8

COOH,

cooR
COMe CF: NHi CN' SOzMe Noz NMef Ni
"See Ref. 24. 'See Ref. 25. 'See Ref. 26. dSee Ref. 27. 'See Ref. 28. /See Ref. 29. sSee Ref. 30. ' S e e R e f . 3 l. r s e e R e f . 32 . rsee Ref. 33. tsee Ref.34. rsee Ref. 35.

- 0 .8 1 " - 0.63 -0.57 0 .3 8 ' -0.28' - 0 .1 5 -0 .1 4 0 0.05/ 0 .1 1 " 0 .1 5 0.24 0.26 0.28f 0.34 0.44 0.44 0.47 0.53 0.60' 0.70 0 .7 3 0 .8 1 0.8/ r.g3k

-0.47" 1 0 r0 . -0 .0 9 0 .1 3 " 0 .1 0 - 0.09 - 0.06 0 0.05 0.02" 0.34 0.3'7 0 .3 7 0.34 0.28 0 .3 5 0.35 0 .3 6 0.46 0.86b 0.62 0.64 0 .7 1 0.88r 1 .6 5 r

- 715b -0.16 0.05 - 0.06 - 0.1 0" 0 0"r - 0.l 0' 0.35 0.40 0.41 0.36 0.32 0.37 0.51" 0.13 0.68 0.87

At

- 1.7
l .- f

The Hammett equation can be rew

logi

_0.92'l -0.78 0.26 - 0.31 0 - 0.18 -0.41b -0.07 0.11 0.15 0.14 0.17 0.42 0.48

so that

-a(
and

L3N

- AG =

0.66 0.79 0.41 1.g8t

0.56 0.13" 0.36

1.00 LZl 3t

For a given reaction under a given se so that o is linear with AG. The Hammett equation is not the o correlate structural changes in react (see p. 452) conelates changes in s relates acidity to catalysis. The Taft r correlatesonly field effects.ar Taft, following Ingold,a2 assume steric, and resonanceeffects will be th acid or base (see the discussion of es Rate differences would therefore be c RCO.!R/. This is presumably a gooc transition state for acid_catalyzed tydr hencedestabilized by _ I andsrabiiiz 6+ 9Hz R- c_oR, OH

l-

and ring systems such as naphthalene3T heterocyclic rings,38and for ethylenicand acetylenicsystems.3e be The Hammett equation \s a linear free energy relationship (LFER). This can a demonstratedas follows for the case of equilibrium constants (for rate constants similar demonstration can be made with AG+ instead of AG). For each reaction, where X is any group, AG: -R Zl nK

while the transition state for base-cat charge than the starting ester. Field e determinedby.measuring the rates of ac XCH2COOR',43where R, i, h"ld.oort could be determined by the equationaa

o r : 0 . 1 S 1o s / l L "\