Hammett!
"#$%&'()*+,-./01234)56!
!! L.P Hammett789:1934)
!! ;0,<./=>?@A*+BCD!
!! EFG,HI)./JKLMNOPOQJ$%&7R
STU-VW./)XY*Z(K)[\]^_*Z(k)`a
$%b)cd-efTU-g)hi7RS!
log(K/K!) = "#
log(k/k!) = "#!
# j$%&*Z-kldW$%&)mn'(JoRp\q;r
:stWuv-Lw\$%xyJzwM{AU|
"j./*Z-kldW./)}~JoRc)ÄÅÇÉVÑÖ
ÜW./)01JhTUáà7âÜdU
&ä./!
K
CO2- + H+
CO2H
X
X
log(K/K!) = "#
!! ãå25 °CJçéUèêFë)2í.
/`&ä-TU
!! ì)./)./*Z"`1-TU
!! a$%(X = H))$%&*Z#]0-A
U
!! îïJlog(K/K0)-pMñDr`óòô
öpWõVú)ùû`ü†!°ïÖÜ¢#
r7£*ÑdU
X = p-NO2 !# = +0.78
X = p-OCH3 ! # = -0.27
!
§•BA$%&)"r
!!ÄÅ
"mn¶ü&]ßW
"mn®©&]™
!!´¨r7ÉVL≠W
ÆLmn¶ü}:[\
]®©}|
./*Z
">0jmn¶ü&JzØ./∞^
"<0jmn®©&JzØ./∞^
ùû±≤≥¥µ∂#hi
$%NOPO∑∏b)π},±≤≥¥µ∂#:∫¢ªº|a$%b)./)π},±≤≥¥µ∂#:∫ªΩº|)æ
:∫∫ªºø¢]¿¡)y>•ÑdU!
∫∫ªº¢÷¢◊ÿŸ¢ÀÕ¢:⁄¢€¢⁄Ω| = -2.30RT Àog:⁄¢€¢⁄Ω|
= -2.30 ÿŸ‹∆
∫∫ªº¢:$%&'(JzU±≤≥¥µ∂#)¬√+|-$%&
)1ƒ≈n∆-)«J]e»hi:ùûhi|7… ùû±≤≥¥µ∂#hi:ÀÃÕŒœ–¢—–ŒŒ¢ŒÕŒ–“”¢–ŒÀœ‘Ã’Õ, LFER|kldU?@A}~!
"+-"./›-$%&7ùfifl‡TU-HammettyJ·‚AL
:„‰ÂzØ./7^†AU|
#r)§‚ØJ"+[\]"-`ÊLU
ÁËÈÍÎy
ñÏJ]./Ì-JÓÔÒ)flÚÛ©)@¶}]{AU
"!ÁËÙı-ÍΈ˜]ìdÜ`¯˘J˙dW
""¢˚¸˝œ˛˛Œ‘‘y>ˇUÁË◊ÍÎ)y`89
À’“!"#€K0ø¢÷¢$("¢$¢–∫∆R+ø¢"
"" #"R+ = ∆$¢È¢∆
:mn¶ü&)%H]∫∆R+, ∆$>]A†∫∆R-, ∆È|
ë2í>&flÚ)Û©É
!!À’“!"#€"Ωø¢÷¢‹(∆Ω¢$¢–∫∆R+¢$¢–∫∆R-¢ø
!!# ÷¢∆Ω¢$ 0.27#"R+
Hammett!)'Ê()
R
CH2CO2H
[1]
CH2CO2H
CH2CO2H
R
[2]
!!uvWst$%NOPO([1],[2]))
%H]… !!*µö$%NOPO[3]Ç+,G
-µ.Oë[4]>]/… b017./J234
[3]
R
R CH2CO2H
[4]
*µö$%&-+,G,HI)%H)"
"""""""""""""#Tafty
5$)≈n`∏˙p67
≥;<µ)∞ã=2JçLM
ë}89¿>¢À’“!k#€k0øA¢÷¢Es
:&}89¿>¢À’“!k#€k0øB¢÷¢$*"*¢$¢Es "
À’“¢!k#€k0 ø¢÷¢$*"*¢$¢$Es "
ñDr!É>J67Ñdùûhi?π4
Hammett!-./01
./*Z$j:@^AB)|./ÓÔÒ)C}`.D
"">0jmn¶ü&JzØ./∞^!ÓÔÒ>™mE`FGMLU
" "<0jmn®©&JzØ./∞^!ÓÔÒ>ßmE`FGMLU
»|
HIJ)ÓÔÒjßmE
HIK)ÓÔÒj™mE`
FGMLU
./01)23
!!‹LΩ>]™mEÓÔÒ:HIK01|
!!‹MΩAÜlßmEÓÔÒ:HIJ01|
NOJ∆÷Ω`PJ./*
Z)ߙ7QR
$%&#)ST>./01
7¬,
UVOW…./
!!#7mn¶ü})X]Y)./7@^
!!#7mn®©})X]Z)./7@^!
˝œ˛˛Œ‘‘!]CD!-]L[W'Ê\]./]Z^»-_ÂJ`L
""""""! ˝œ˛˛Œ‘‘!)a5`bcMLUN≈