niodi~a~~d~rnaul~l~`1tli4~ai~d~flicarlr~u~n~~ ~uuBu dgn~b~aqa

J
d f i % ~ d ~ ( i U n ' ~Lf l~
~%
(conjugated
I fI ~
double bond) ~ I ~ $ W I UJnm~au
~
A i
NI)JI~~LRAOU~~&OU~J
(delocalization)
3.
n i o d i ~ a ~ ~ d ~ r n a u l ~ l ~ ' 1 t l i 4 ~ a i ~ d ~ f l~uuBu
i c a r l dgn~b~aqa~illu
r~u~n~~
G H r ~ n a m t ~ u ~ a q d u ~ d ~ n ~ uri~:arnauua~tl~fuaudlul~n~urnirad
~duuu~u
~ d ~ a r n a ~~ria:arclouaa~~ifuaud0=:~0u1)a~tlif~au~ni~a~~a~u'1~~
u
re~6~arnau
*iuarddau~:~11~acnau~
o ~ t l iYf O ' U ~ U ~ U ~ ~ T~raramauuo~tlifuov~utlif
~QM
uau~flu
Y
V Q ~ C ~ ~LL(I:U Os-orbital
U V O J ~ ~ ~ ~ I Luansinu
OW
J
uh~~darorcnauua~tlif~au~~d
p-orbital / i ? ~ hrrda:: p-orbital d~1iuiir~nnrau~u~ifq
d ~ a i u i r o ~ n b a u d wp
o
~m
~ r fi~~iiud;
~ l i u ~ r ~ n n ~ a ~ ~ ~ ? ~ i u. u ~ u d # ~ ~
v i w a r ~ n u i d ~ ~ f i nsp2-orbital
~in
~ ~ ~ n n n . r a d ~ ~ ~ ~ u A i i ia+
u ~2 mido~ in =
a ii n
riusrd8aiua8un'uflunr~duq
~n~
1
I
~ u ~ ~ ~ O J L U U ~ U L ~ ~ U ~ ~ ' ~ 7.1(n)
O J U L~Lq~t (v)
~ ~ LLI ~LAW
: L UL U~U~L ~
WU ~ ~ I ~ R ~ J I ~ I J
i
I
:
L T ~ L L U (resonice
U~
structure)
~~~~u~utaqadijn~~~~i~~di~~~~ar~a
5
d.rmir d~sn'udd~~~d~uo~w~uii'~~"nmfau~uf~u"u
~ O ~ J U K ~ I ~ ?
I
~namruuulmuuu~d~8~niw
r.i(n) ~ S a r n w7.1(a) rrddhamzrflugn~au?~a~~~uu
h-
7.1 (n) UALLLUU 7.1 (v)
i
~ U L ~ ~ ~ V O J L ~ ~ ~ ~ ~ U
u r
k ~ ~ ~ t i ~ ~ u r a g ~ n u ~ s r ~ ~ a ~ ~ 7.1
u ~(tl)u d$4 ~ n ~ m r 2 i ~ n
L i ~* n +Li ~ ~ W L U U ~ ~ U
(resonance
Y % ~ hybridj
f
CM,287 (H)
117
d
nisnnasjn 1 naiu~iui.r~lrsni.~a=aiu
lrni i d h 1 ua. a ~ l u ~ a a m n a a aMU~LLJUBUFMI~
~
3 MU^
4.1
LU~I
Wj~nndiaiy
# ~ ~ ~ ~ ~ ~ ~ ~ Z ~ I U L ~ ~ U ~ ~ L ~ U ~ ~ ' W H ~ ~ I ~
Y
riini7nmaa~hl~ul3~ufiiuna~l7~~~fiz~aniuocl
I
~
L
~
~
~
~
~
J
L
~
U
~
U
~
~
~
~
H
~
~
~
V
D
~
~
A'
disdao7zuiulu~aqa n ~ u m u ~ ~ ~ n n ~ a u u ~ ~ n ~ ~ ~ ~ ~ ~ u a ~ ~ ~ . i ' ~ i n ~ ~ d ~
1)
-1
o ~ u a a ~ ~ u ~ z ~ f l u d c i a ~ n i ~ ~ a ~ ~ i ~ d n a u ~ ~ I n n ~ ,a u 6 ~ f ~ ~ ~ ' d ~ I n 1 n ~ ~
f i ~ u C 4 i ~ u d u e z d w ' u z z~~a ~ ~ ~ ~ l d i 1 d f i n t w n 1 7 ~ 6 ~n71t
~si~~d~8~fi~
dfill5u1n~~~~u~z1ddu~~u~~~~fluai~~6nn'~(n'd1~1iiu~w'aun4iI~
M ~ U ~ L ~ O ~ ~ J W ~ L ~ ~ h
~ aUl hU~ Ut d~u d
V ~~~J3 ~u i~nLi 7U tU~ ~
~ lUm ~ l ~ a l ~ 1 7 ~ 0 u
(hydrogenation) ( ; D J V ~ ~ W ~ 5.6
J ~ I~IRU~~DSL~~L~~U~YU%U~H'LOU~IIICIRL~~'IIIICI~U
U
(cyclohexadiene) ~ J ~ U ~ U ~ ~ ~ ~ U ~ ~ L U U B U ~ D ~ ~ ~ L ~ ~ C
H
E
benzenonium ion
(7.3)
H&
rAnrflubenzenonium ion B J ~ ~ ~ ~ ) D L ~ U X ~ ? J I ~ ) U ~ R benrcnoniuk
H A U Y O J ion # k U
d f i f i ? u l u a ~ R ~ L ~ ~ ~ ~ o(Lewis
~ d n ~acid)
~ 1 ~ ~d~~l(ftnfiaal[.ri1iZu83if3
3~1
dfifi3u1
/
7.a.i.e JijiiiuiLLnJit
dfiR5~1B5~a~u~iZudfifi5u~~o~~aZw~u~~6n'u11.rd.rznouar~.r~uiin&uu"n.r~15j~61~~ua:~u^u'ufiao~.r6
~~zu~+A~~~~RAP~IIH'M~~~zR
a
~nlzn'u?~~uuilda
ounln.rlvtflud~fi5~1diia
n?flu~hu'looou(carbonium ion, R + )
d3lii~lnd~iii~l,zM-i73~afia~n~a6n'unf
a 5 j 3 ilfifitmd6uwulau Charles Friedel UR:
James M. Crafts 1~~7~n40dfifi5~16h
dfjfit~nl(?l~1(177dfiI6~~8~63#~
(Friedel-Crafts
Y D
4
alkylation)
d
BJ~Y"U~OUKJX
RC[
+ AIClp
=
&
Al C1;
+ R+
(7.7)
R
H
(7.8)
1
120
CM 227 ()I)
I
7.3.1.3
dfiiiiaiiYa~dt~#~
undhu~~akt~ofln~oon1'11A
nsol$~~??n#d$arvlofla~aom'l.a
ng sulfuric acid)
~fa'l6qinn.r a
A R ~ ~ ~ ~ ~ ~ ~ I ~ ~ ~ ~ ~ u I K U ~ O ~ ~ J ~ U ~ I ~
(7.1 1)
U l ~ l L n ' U ~20 U I . 13~UHI~Rn@€lCI3 L ~ u L L I u ~ u w ~ ~ ~ ~ w H I ~ fRD ~~ ~~ I U~ C~ I~ I ~ H u ~
Y
D
urn1=mudasu~h~3~8~~uada~d~uflf
LI 10 HUcl n 1 r a U L ~ u h L?fr f i U ~ d ~ ~ L ndiphenyl
'R
6
anhydride)
halide) n n l ~ u a u l u l a f (acid
lfl~h
~Jfllf
Y ~ ~ ~ I V O J D Y ~ 91LflUlLIff
U ~ Y O ~ ~ ~
Y
a i ~ ~ ~ m a ~ ~ ~ ~ ~ a b u u ~ = :ac~liurn
a ~ ~ion
u afiaunif
n i ~ z 7.16
a ~ acylium
q ~ n ion
' ~O Y ~ I
~ c i i A ~ f l u ~ ~ h l n ~ b f l u d ~ n ' f u i u n7.17
u d 6n~~al ~nn~i a~ ~ d i j ~ f u i u n u d C ~ u ~ ~ ~ a ~
;fit
0+- A1 c1; 0- A1 c1;
0
U
RCX
122
$ AICI3
U
[R-C-x
I
R-C-X
+
]
(7.15)
CM 227 [H)
,
7.3.2.1
r
14 va
nt(n1nstbnclmu (electron
releasing group)
J
~Oua:aa~~ia~a/a:~~aun
riasamd.r:guanlua~~uu8u rl11$miflu~icuu'laaaud~iim4u1u
transition state dnaiu
3
14 u. a
~abfulnuw B ~ d ~ f i r i iactivation
lri
energy s ~ f id ~
On~ui~~nuddd~Unl~a~sna5~u
am a
tw a
~ ~ ~ 6 nan.hd~~i!tli~~nudlu~~uBu
lhif
M~dl~a~wna~aut!~d#o-h
H~L~U~I~IUI~J'L~(activating group)
Lum
~ i f l ~ ~ i ( ~ ~ ~ I ~ ~ ~ ~ d ~ (E)
i j ~I ~~mi inz d~rLi i u
# ~ndl~nafalf d
l nd
JA
I J u. a
u s z w ~ ~ i l u ~ ~ ~ u d u n a ~ a i f d f : n a u a : l ~ ~ u ~ n n ~
~ y14
n kua.~as n a ~ a ~ ~ : W c # n a ~ a u ~ ~ ~ n i f u ~ u y 1 n a : a a u l ~ a ~
~ u u ~udazaauva~nif
u
uaudIn~d~m0:I6~u^0~~na'~auuind
fi8uniflu~duu
aantl?ruuwuniw
7.2
Iaaau~uw~av
III us: VIII ~ ~ i l n a i u ~ a i i u ~ u
$ Ji n
Ld
~~
~~H~IGL~~~I~TIA~L~I-~
riiu~d~aaflnusrcnsil6~f
an~i~ni:deii~~~ri,d~uaq
&#u$dtvl~l&di~
riiu~ddaaflnus:wifi
J~'IH~L#~QI~~~O=:~'IH~QI~H~L~~~~'ZIA~~
ud~mu~a~du~t#n~nf~~l~da~~~~~:~d~
aafln ~w~i:drii~~~~oaflnu'n~z~iimni~n~:nun'u
(steric effect) vosn~uazaaud
~niza(3nflulua~~uu8u
~ a j d I ~ ~ ~ a n n . r a u-lR.
6 ~-OH,
~ r 1 -OR, - N H ~ , - NHR.
- NR2,
- NHCOCH,, -SH. -Ph (fiih
-
,
-
I
124
CM 227 (HI
Ar 4
7.3.2.2 M ~ ~ R J D I ~ ~ ~ (electron
A I O M withdrawing group) L~UOLIIO~M?~M~/OL(IOU
(1
d~Aud.rr~u~nlu,~~uuGu
~ ~ f i ~ ~ ~ f i i ~ o ~ ~ u u ~ a o otransition
u d ~ i state
i m Giin,iu
u~u
~a8u.riiaua:
c.a m
u'~diiIrr'activation&ergy ~bjuG;d O n ~ u i ~ ~ ~ u ~ ~ a ~ ~ i ~ d ~ : : n o u o r 1 5 ~ u ~
d ~ ~ l j ~ ~ ~ t ~ n n ~ o ~ n ir ~ o ~ \ u ~ ~ ~ y ~ % u ~M~II
~IJu . ~ ~ ~ n m l
A
dA
& ^ o L ~ n n T o u o J u % o ~MI&Wn?iudod?
l
(deactivating group)
w i ~ i d ~ ~ ~ u u l u u o ~ n i ~ d ~ r n a u ao ar;l ~ ~ u ~(GI
n di n~ i ~r odd dr i omu~ LLamJ
~~ann~u
l i l u u w u n i w 7.3 M ~ ~ ~ J~ aB uL~ ~~~ w
I " o ~ R " n ~ 1~5 oo u ~~ i nn an ir fn a u ~ u a ~ ~ u u ~ u
*
u r i o r n o u v o ~ n i f u o u d a ~ l i f ~ ~ n m ~ o ~ n n n ~ o ~ ~ r ~ n ~ ~ ~.&~w"u
~~ncn~ouuind
n i f l u ~ G u u l o o ~ u ~ u i uxrr
~ a u_ a .z v m a a u ~ V I $I~ i i n a i u ~ w 8 u ~ h s d q9R~ f i ~ I 6 '
7
<;
,
niflu~~uulooaud~ii~~inni~~niruo~E~6nln~lv~id~ii~~v~oaflnii~n
I
,
(
8 n & u ~ ~ ~ m f l u ~ i u u l o o a u ~x~ ua:
i u: uXI
o niflu~~ualoooufhiimiinni~~nir
I
~a~l~~n~n~~~d6iu~d~wif1~::ij~nwm::d~0u~n~iu~o~nir'~u~iiuu1oo
XVI Lbar XVIII uamflu~iiuuloaaud~fia~inni~~ni::~o~^o~4nln~l~dd6i~~~d~~u
~ r f i r S n ~ m r d ~ ~ ~ n w a u ' ~ a ~ n i f l u ~ i i u u l a a M~IULRY
o u t ~ ( ~ iXIII.
u ~ ~xrv
u u ~ua::
a
xv uardftlu?n~mrr~iu~dfdnif
~ a u l d i t ~ a i u a : : wriilfin~nlnnirua~
.
I
XIV
xv
wuniw
&y
.
7.4
Tj.
H
E
H
E
+-
XIX
Q~IUH~J
~nitn
rl
oonn
XXII
rniiuruin
kH
E
,
xxv
.. XXIII
XXVI
drumn
XXVII
7.4
&;;diquM~ml
E
XXVIII
XXIX
Id~uOor ' , "
rufiur
rn~m~~~aaaudu'~~n1~~81w~~u~n~=:a~n'ou
Y
8
11..
~finlutransition state dnaiu~u~u~uindyn
n~uud~n.rui~~nud~ua~~~u~wdd~~or~
I - *
rl
w a
dl~~Wnn.rouor~fin\n~.ran~n
dau~~a:noudn~o~~nn~ow~::$il3iniflu~fiuu\aoau
A~finIwtransition state dn~iu~aiiu~iioudyn
~~ii~~fifiiui~~nu6'Iwa~~~u~wd
ww
rl
ornoudn~o~ann.rouo:~fin\a%inyn~ d o c d ~ u l n ~ u u ~f wn ~i~w~ou ~ a o u9ddllld
i~
1 1 1
A J
E~Iina.rou d~fi5uiunudo:~fi~~uo'~.ri~fa\xi~~;ifiu
a~uuod6unaiu~iui.rn'Iwni.r
. l i ~ u r ' n ~ i ~ a f i u . r n i w u o ~ n i f l u ~ ~ u ~ ~ u \ ~ l~ui4ni u
h ou~~~~~uu a~ fllnu l u
I
r
a
u.r.rni~ia:aoun'i~q d n ~ o ~ 1 n n . r ~ u u " u o t u " o ' ~ 1 . r i ~ f a ~ o ~ r ] ~ f i ~ ~ i ~ ~ n ~
l
a
w
a ~ ~ u n a i u ~ ~ f l u . r r o ~ n i ~ u ~ ~ u u ~ andi?#o
o o u ~6ignn~o~nnnrou
iduin~n
uinniiilonu~u.riioun414ilfifimdfiFi5ui~in41~l)unic~ d a i i ~ ~ o t r n o9 u#J:JHUR
h~
rl u
d ~ \ & ~ r i ~ d n b o ~ l n nHr~dR'dttnrn.rau
ou
u n e ~ ~ a i q u a t ~ ~ o u u n d ~ u u ~ Cai u u ~ n . r ~ ~ f
CM 227 (H)
ioun:ao~wnwdsn~naa1jm~nau~11~2
(mchlomnitrobenzene r i ~ n ~ n a u t ~44'n a?
o-chtomnttrobenzene i
nuiumq &u4krlu
CM 227 (H)
j m ~ n a I uM R ~3 2.5 0 LLnr pchloronitrobenzene C ~ ? B ~ M ~ BIMM
U 8i d)
25
n i t titCuGuim3 ro an. kudrruxu
I
n i ~ n a a e ~sd n i ~ a d u u a i l u u Q ~ i i C a ~ ~ ~ d ~ ~ u i 1 u ~ i i 1 ~ f ~ l ~ u 1 ~ d 1
szlsiuGn
1 ~ h ~ n f \ v ( f l u d ~ i i ~ u i ~ u f ~ ~ ~ # ~ o i ' 3 ~ ~ ~lu
~~d~o~~~~
n i ~ n n ~2o ~au o ~ a n 1 n ~ \ ~ l ~ ~ = : o ~ ' 1 u ~ ~lu~b~Ruu\aoou
u o ~ \ o o o u 8 ~(bromonium
~~un~~i
ion. ~ r + )~ ~ ~ i i n ~ i n d j i i ? u
u"u~LR=:nfno=:~8n
l % ~ ~ ~ u f 6 ~ u u n i r7.23
Brz
+ HOAc
.lli------
HBr
+ Br+OAc'
ui~d~=:nouorl~~u~nd0=:'I5nnuouiio
acetanilide
p-hydrorybenroic acid
rrl a
R LLI
(7.23)
L U U ~ ~ A O ~ T L U U ~
=:lnfl; w
~mm c i i ~ a o n n n ~ o ~7 uHROR
i
U
II
~ ~ ~ ~ i ~ u a ~ ~ i ~ ~ ~ = : n a u o = : ~ ~ ~
4'i.s~udiinaiu~buic
0.2 ~ ~ ~ i ~ ~ u u i ~ ~ = : ~ i ~ ~ u o ~ 90%
n ~ AnJ o = : ~ ~ n d ~
7.1.2 ~ ~ u ~ u u a : l r l l 1 m a ~ u n 3 u
7.1.3
1n88u~~at
styrene
7.1.4 Luu~uu~~::
styrene
1.2 O J L B ~ W ~ U ~ I ~ L ~ G L L ( I ~ ~ ~ I ~ L ~ ~ U U ~ ~ ~ ~ ~ : : ~ O
7.2.1 p-chloronitrobenzene
7.2.2 m-chloronitrobenzene
7.2.3 p-nitrophenol
b a
7.2.4 p-chloroacetanilide
7.4.2
~~I~LU$U
7.4.3 Friedel-Crafts Alkylation
7.4.4 Friedel-Crafts Acylation
7.5
~ ~ ~ ~ ~ ~ d a ~ n z 1 m ~ ~ ~ r ' 1 ~ ~ o ~ a~c184 ~ ~ i j 6 1 n ' t ~ w " d u n f ~ n ~ m ~ t l ~ 1 6 0 1
(mononitration)
7.5.1
2
do~ifdfzno~daIdu
lYfruLYuifu
7.6.2 b @ U
7.5.3 aniline
7.5.4
IulvlfL Y U ~ ~ U
A
7.6 PJLG~~L~IQJHUIU
+
~ i r dtnou
r
cofinLuu4u
I?Qn~uu%u
phenylacetylene
nd~udadnudgjnflll~ii~~y~
LLILL~UL~~DJH~JIU
- Iu~o~"M~R
84-
r r n
Y
Brt/CCL
Br2/CC14
Iuiim
Iuddum
.........................
........................
........................
A
113B r n l l l
A~(NH:,);
........................
........................ ........................
..................................................
aesluumof
........................
........................
........................
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
-
niawnaed r d d 6 i ~ i ? ~ i ~ % $ ~ % @ r n ~ 0 ~ 3 1 f l ~ < ~
dua;lwa"nwnjoinni~mnwn*ndi~~da
.................................................
diwlnl~rmot~ninui~~d~~m5"~~~6~1nnim(i\no~
= .................................................nS11
~iuimuatnmm?uninleue~d~$
- ................................................... ua.
-- .......................................................
Jun
- ...................................................ua.
- .......................................................I l J a
- .................................................. ns'u
Jiuimuoqnm.tinija3n~4~4~d14
Jiuimuo~nndnuu4ufh4
= ii'iuaranfu =
............................. lua
u.ufumqa
fidIfldfflJfi~Mfldial1~
(limiting reagent) nB .....................................................................
&4
:. Jiuim.uo~~i.rwrimn'mcy1~1na~~m5"~u~dimiuw~'1~=
................................................3ua
4
acetanilide
~uw4w
maoTr~uwQu
p-hydroxybenzoic acid