.

Aldol Eondensation

Na

.
→

"
" "

aldehyde
"
aeldol
aldehyde + alcohol

Mechanism
Resonance
"

:
J
-

,
,

. ! .
→ ,
.
" "
aldol

" "

Heat .

"
→
J → "

Ena )
"

=
fAlkene + aldahyde

Ch 12. Carbonyl Compunds

urnony "

ex ]

AmirePlans
.
, sp pesonance ( )
uyende . e.
"
st , , =)
5

*
+
*

*
even I
.

Irucleophilic addition to Eatbonyl compounds .

¤
.

carbong )
.

evis
| base
-

,
, Impoftant Na
+λ3

arban ionns ! ,
-
1

! NaB ↑=
:
,

,
a 1 mPOkTan +XN

lh .
p-
o udenide "

Earboxylic acids
.
L : lt114 : reduction
, 10 alkohl
este

Lithium alumimum hydhide [LAH )

strong Nu & Base => Nu af Base .

-react Violenty withoo r RoH .

juechanism

+
,
~
. "
↑ . ↑ .
| Eb ,

1
HH
; JS
BNol 04 +
R

.
IVaBr14

p Strong ru & Base

less rea ctive and less basic than LiA 1 r14

aldethyde Redikcfion

ar
,
alcahoss
(ketone

ex )
NaB4.

- 20 alcoh
. . .

. ←
.
. akoh

-
Mechanism

"
' ., .

organometalic compounds

s Com pounds contain Carbon -

metal bonds .

si iyt -

gi ⑲ -

IM =
Na
,
K 14 :
/uS 2i 197 =pb , sa ,1g
,

iopic bonding CoValent bonding

' J
 .

Gtignard eagent

pfep
capbaniop
σ -
k -

x + oyng +
-
o - → R ++ s
pingt I R ; Mg ,

ex ] Ar - * + g → ArJ g α

Reactions of RMgX I RLiX

t
88 sts
'

r M9 .
☆

- . + M 94
H
→ pH
-

+
+ ×α

(y =
0 , 1v, 5 )

I ] CH3 MgBr HzO 14 of ugzt* Br

γ

+ -
> c + +

ω
MgB

KO
-
)
>O
2
' ,cBoM + 3 o- + Mgzt + βr
γ

3)
≡ + <
BMgBr → C r 14
+ ~=
- +

Mgzt
+
Br γ

Ghignard with epoxides Icclosed ting sthucture)

√
=
alCohol synthes ;s

pngBr +
. ,
vor

mechanism : Ring opeping txn

β lugBr + RN ,
↑~
-

→ ∞

√ akoh .

C . f ) 20 alcohol

+→
".
R -MgBr
↑
. …
'
"
- ngBr n "

p
pT
+
+ →
.
μ
.
kxIN rwithCabosny ) compounds

n p
,
+ pMg α
chigbard
'X "
reagent

/Mechanism

+,
π . n .
. .

alcoho ]

Retho gymthesis
{

aoay
.
RIMgX
- -
"
.
1)

.
bm
*

oH
)
n "
β
' s
(☆ u9

) HT
,

Retrosynthesis of alkohol .

!
"

P "

" ,. ug ×
-

* .×

~ R
"

R 6
~

RMgx '
p
H

Mechanism

∞ ,
'

" "

'
-

"
 -

conjugated system

ofbital )
" "
-

invalves at least one atom [ with a p

"
bonp
"

adjacen+ to at least one π

" "
-

a system of conmected p orbifals

-
al teprating single and maltiple bonds or Jope pairs
A]
ex)

e × . =
.
1
on di 1 enone enyre
= alkene + ketone = alkene talkyne

1mporfan + proparfy

pelocalization of electron
∞ 0 ←) ≈
I
.

Resopance =
stable

1) biene

~ Ψ ≈
1 3 -

butadiene 1, 3
cycldhepadiene
-

,
2 4 .
.

-Hexadiepe

2) Djynes

2 4
hexadiynes
-

3 ) Trienes

≈
2, 4 6
bctatriene
-

C f]
.
Conju gated system

≈≈ .
,
n

.
Relative stability of tesoman ce sthacture

13 The mote covalent bonds a sttuctupe

bas the more stable ; + is .

π , LX
mare stayle

≈≈ as vo
+

more stable
2) charge separation decreasesstabilify

3:
3) The sthratares having a complete valence shell are especiallystable

+
1 ←
,

.
kipetic us Thermodynamic Conttl

Inajor rxN =
IG .

≈
BK
> " "

what is major prodact ? activation energy B Majr

AG ( Thermodynamic) "
<
B " Majo
E

prodaction rate : B 77 [

{ Thermodynamic stability : BEEC

=> najorprod

temp
" "
, how =
3 B is majar produst .

( )

"
High product
"
2 temp =
, C is major .

" "
-

.
[ Thermodynamic Control )

.
Addition reaction of Conjngated diepes .

1
≈ ← v
=
low femp 1 2 -
addition 1, 4 -
addTtion
,

725
'
. ,
f Low T Kipefic con+

)2
.
-

addition
-

Mechanis.
ReSonapce

+
H- , K←
wat
←,

|
√

'
2

1
 -

kKjnetis Vs thetmadynamic conttol

Br 20 % %
w*
≈*
"

+≈ KipeticContr "
Br

nIBr →
Hign T
Br 20 %

0
t "

* +ΛN ThermodynamiC Cont

"

.
-The Bie 9 s

- Akerreaction :cyKliCCompounds

-
one step reaction for Eyclis compends
←

, LIn
E

λ F ITENE → Ena ET
"
"
"
"
diepophile
.
diene
=
↓ ieme

+ EWG

EX ]

, .
* …
Lis diene
' "
" "
dienopbile

,.
F - ,
.
"

diene
" "
"
Trans diene
-
-
s Cis -

biemophile

EWG - 3Halagen , LI σ COR COON COOR

/
, , ,

focns
.
CIN , Ah Eo -

0 -
Eo
,

m IFEN
1
T
'
t -
lCotbcts
I "
.
opypoate
,
"

NORNEI
"
"EINIPHRRak
" "
"PKRNIie
"
netnil
KENe
,
L nakl anrprie

.
Stereochemistry

1) syn -

addition

z) The configuration of the dienophile is

retained in the produ.

* -:0
e × ne
): + → IT7
√Me 0

Eis -

fatm
<i5 -ftm .

33 The diene reacts in thecis -

farm rathet than in the tfans fotsm
.

Aromatic Eompounds =

kns ? .
s
*- ortho
"
mexa
"

uane "
xylene

..
a

Pn
1
" "
" "
benzene Sulfor;c acid
." aniline
-

"
"
"
Benzoic acid
"

acetophenone

phepy / group : [CEH5)

"

1 -

pheny ) - - butene 1
"

benzy/ graup : metny / group

-

" "

Benayl chlofide

HeteroEyalic aromatis compounds

× λ
" '
"Thiopane
"

"fatan
" "
"
pyridime
"
puyrrole

by eschancesttaatzere

.
RXN of benzene bepcene γ .

. Br Bs
Br

.
" nera"

β π .
electroprieINE
+
-

"
Ee +
electfophilic
! →
+
subst;feti,

-
uechanigm NxN ↑
Resonance = :

" [ . , ←] →
 )
! +
ex
→

a+" s

-
Mechanism

^
Bγ -

Br + FeBB -
s Br
+
+ FeBr4
.

,
,
]
'
← "
←
"
F
→βγ :
-
→
, HBr f FeB .

Catalyst

.
/Nitration

Nen
s .
-

IMechapism

0- +
-
.

*
← . , ]
N0s

→
K' .
K + H30 t

.
Sulfopation

.
st

uechaniss
-

+ - ± + Hsos
-

+ [ , I
,
-
sst +
Msx
.
Fridel -

craff rxn

F <
-

AlKylafion

+ *
s
aq
↑+ y

K
-

syechoanisn

- it
+ ; →R + ,

+e .
[ + ,] , !

' * → *

!
"

+ Λ ,

√+ 510 Eatio?

cation 3
K 20 at
* ( 20 →
,
.

F L
-

acylafion

"
.
↓

[ " 'J ←
"
.

etprerone
ch☆

" , .

"

OTh important reactive carbocation

1 .
HKepe

- → ! →
2 .
AlCohol

- " :
☆- BF
H
δ

+
-

β ,→ ,
, BFs + on
.