w , ; - - b.

p -
w pKa pKb , ,
pKa + pKb = 14
w pKa
HI

-10

15.7

HBr

-9

ROH

16-18

HCl

-7

R-COCH3

20

H3O

-1.7

25

HF

3.5

NH3

36

CH3COOH

45

H2CO3

50

,HCN

10

w : pKa - -
( )
w
w ex.
w ;
w ( -)
w : 2>1>3. .

: 3>2>1.

w : 3>2>1. s-character pKa . .

But, s-character .
w - --
6.
w :
w
1. .
2. (= , : 4 )
w : (+,-)

w (o.p) =

w
: 2,
: 50:50 (=S R 50:50)

w R,S:
R, S
R,S
w E, Z: Z, E.
w : . (RR-SS) , ,

, . (n: )
w :

(R,R-R,S)-

, -

- ii ,
w !

1. alkane:
2. alkene, alkyne:
3. R-X(): E1, E2, SN1, SN2, E1CB
4. :
5. , :
6. :
7.
8. /

3,4. alkane

alkene alkyne

. alkene + /Pd (or Pt, ) -> alkane

( ,)
:

: , 1<2<3
E = ( E 1>2>3)

alkane

. + -> R-Cl + HCl
alkane
. alkane+ -> +

) Br

allylic position( ) : . (-)

: benzylic position(-Benzene)
HBr
1. + HBr ->

(Markov)

2. + HBr/ -> //Br

: Ea , ( Ea r.d.s .)
kinetic isotope effect( ) : Ea data
r.d.s.
propane : Br
Hammond : E !
Cl Br

- iii Cl: , 12 -> X

Br: , 12 -> .(2 . Harmmond )

: , , X
: , , .

7,8. alkene alkyne ,

1. (carbo)

. R-OH + (or )
-> alkene +
carbocation: (+), , ( ) 3>2>1 (carbo )
4
3

: (Zaisev rule),
cis trans.

2. HX

E1 -, = k [R-X ], carbo

. R-X -> X(L.G), carbo (r.d.s) -> () ->alkene

Good L.G: ( ) 315p
RF << RC l< RBr <RI (-Good L.G)

E2- , = k [R-X] [] carboX

. C-X C-H H X ()

E1CB- E2 , (F) carbo .

E1, E2 4
- kinetic isotope effect: H D . E1<<E2
- carbo : 1<2<3, E1 only
- anti-: E2 only
- : E2 only

alkyne -
alkene : (14): +

1. - syn,

2. HX : carbo,markov

: alkene+ /Pd -> alkane

(Markovnikov rule: H H , X .)
. alkene+HX->alkene-H(carbo, r.d.s) +
-> X-alkane-H (

3. HBr anti-Markovnikov : . (, ,
)

: NBS alkene

- iv . alkene + NBS/AIBN -> allyic (alkene ) Br

4/5/6: Markov ROH , 7: anti-Markov ROH

4. ( ): ( ) OH . Markov, Carbo
: , Carbo

5. : OH . Carbo , Markov

6. carboX-,Markov

. alkene+ -> , carbo ->

->

7. (anti-Markovnikov):
carboX-, anti-markov
. alkene + -> syn -> -> OH

(anti-markov )

8. ( ) : carbo X
1. Br

2. . anti

9. Halohydrin : . markov.
. NBS, ,DMSO halohydrin
. halohydrin+->alkoxide->SN2->epoxide

10. Epoxidation

(MMPP or m-CPBA) + -> O

1. / : (carbo )
2. / :

11. carbene( , cyclopropane ) -4

F () + ->
F + ->

F + Zn(or Cu) -> carbenoid (carbene)

F sodium trichloroacetate-> + + NaCl

12.
Syn diol

alkene+ ->-> -> syn diol

alkene+ / ->syn diol
( -> ; alkene )
anti diol
alkene epoxidation -> +/ () -> anti diol

13.

alkene + -> /Zn -> aldehyde(ROH)+ketone(ROR)

+ / /Zn ->

( )
alkene, alkyne

- v alkene+ /hot/->
, carboxylic acid(=ROOH)+ketone

alkene+ / /hot ->

alkene + +
alkyne+ (or

/ )-> 2ROOH

alkyne+ / -> alkene +

14. 1,2 diol

syn diol + (or ) -> ROH

alkyne

1.
alkyne + 2 -> alkene -> alkane
alkyne+ +Lindlar Pd(or P-2)->cis-alkene
alkyne+ or or ->trans-alkene

2. HX, : alkene .
3. (vs )
alkyne + + () -> enol (Markov ) -> keton

4. acetylide ()

+acetylide->ROH
: 1, : 2, : 3 .

5. alkyne

9. R-X ( )
: X -R
R-X

1. -HX , ()

2. -()

3. R-X

. ROH + HX -> R-X +

, ()
- Grignard ( part)

: , (
+1, -1)
:

: .

(R-X) + ( ) -> (RY) + L.G( )

SN1( ) carbo

- vi . + -> + HX
. 1
2

-> carbo + (r.d.s)

() ->

v=k[ ]
r.d.s 1 X
3> 2> 1

carbo

: + carbo (r.d.s)
: (RS 5:5) ( carbo ) ,

SN2( )

. R-X + -> R-OH + ()

v=k[RX][ ]
(ex. )
1> 2> 3

: !, - DMSO, DMF, HMPA( )

: R,S ( )

- , -

>

ex. >

(ex. O)

ex. > > >ROH>

ex.

> , : (L.G) . DMSO( )

1 R-X -

E2 SN2
E2
E2

2 R-X

( , , , , )

3 R-X - , SN1

10. (aryl)

,, 4n: (anti-aromatic)

, , 4n+2: (aromatic)-

o, m, p

aromatic: , , , ,

- vii
anti-aromatic: ,

, , ,

non-aromatic: ,
-EArS( )

. benzene () -> aryl-E (carbo, r.d.s) -> benzene-E + HY (E H

)

1.

. benzene + / ( ) -> benzene-

2.

benzene + / ( + ) -> Benzene-Br

benzene + / ( + ) -> Benzene-Cl

benzene + / (or ) ( ) -> Benzene-I + +

. Benzene + / ( ) ->

Benzene- + ()

Friedel-Crafts

.Benzene + R-Cl/ (carbo , ) ->R-Benzene

: carbo
(: Benzene-//but Benzene-< )
1. Wolff-Kishner (12. 5) - acyl(O=C-R) (C=O)

.

Benzene+acy(O=C-Cl)

->

Benzene-C=O-R

->

/KOH() ->

Benzene-//
2. Clemensen - acyl
. Benzene+acy(O=C-Cl) / -> Benzene-C=O-R -> -> Benzene-//
3. Thioacetal (12. 7)
. O=R + 2EtSH -> thioacetal
2. , , ,

: diazotization ()
3.
:

Friedel-Crafts

. Benzene+acy(O=C-Cl) / -> Benzene-C=O-R

( )

; -> . ( o,p, )
- !!

, , , (o,p)

- viii

, ,

(o,p)

(o,p )

() . ( )

(F, Cl, Br, I)

(o,p)

( , m )

, ,
,
: .

ex. Benzene

(m) Cl(o,p) meta . para

- .
-
()
3

aniline + /
aniline
. + / ->meso
. +

-> .

para

para

ortho

( / ) para ortho . para

(SNAr: sp2)

: --

. + () -> Cl , o,p
(r.d.s; o,p E.W.G ) -> Cl

1. o,p E.W.G , E.D.G

- ix 2. F, Cl, Br, I
3. diagram

(benzyne) : -

. + // ->benzyne(3) ->

1. kinetic isotrope effect
2. o,p E.D.G
3. F,Cl,Br,I .

(I )

4.
5. diagram
-
. + (or )/ -> (benzylic H COOH.
)

. -ph + / Rh/C(,) ->

-wolff-kishner, Clemensen, thioacetal ()
Birch reduction

. Benzene + Na (or Li) / ->conjugation H ()

1. (E.W.G) + Na/ ->

COOH , conjugation

2. (E.D.G ) + Na/ -> R ,

E.W.G . ( )
E.D.G .

aryl diazonium

. Benzene + ..... ->

1: (F, OH, CN ) ,

ex. + CuCN -> ph-CN

+ -> ph-F
+ -> ph-OH
I (: KI), Cl (CuCl), Br (CuBr), H ( )
2: . (
)

Kolbe reaction -

.
.

->( )

- x -

hetero

pyridine

(,N)

3-position

pyrole(,N)
furan(O),

2-position
4-position(
)

2-position

thiophene(S)
, , thiophene
: N,O,S E.D.G , .

: N inductive effect()
,
3-position: N + X..

Benzene + : 5 8 ( ,)
Benzene + : (C3)

(Benzene ) , :

. + /, ->
+ /Pt ->

, 1( )

,
(80): 1( ).
kinetic control .
(160): 2
thermodynamic control .

11. , , ether,

R-OH: , Ben-OH: , R-O-R: ether, -SH: , R-S-R: sulfide

: ,: , ether
:
-OH : -, . ,
( ,

- xi

Ben-OH : . ortho, para - E.W.G

-

, syn diol, ()

-, , ,

->
1 -OH

<-

<-

->

<-

2 -OH
3 -OH

->

/ : , ()
ester : LAH ()

Grignard

Grignard : (-) - ex. C Mg

(-), .
-OH: Grignard (-) aldehyde ketone O

OH
+

for
->

->

->

alkene

(6)

. R-C-OH + /pyridine -> R=C-OH
-E2, 23

HX HX RX (3. R-X )
. ROH + HX -> R-X +
HI > HBr > BCl > HF ( )
carbo
1 SN2
Lucas
: Cl - 123

- xii 1OH SN2 , .

2 3 SN1 , 3 - 3
ROH RX
R-OH + / / -> R-Cl
R-OH + -> R-Br
R-OH + -> R-I
v 1 OH: SN2 ,
v 2 OH: (ether )
v 3 OH: SN1

tosylate, mesylate

, : OH .

-Ms

-Ts

->

,
,

1
-OH

->

.
<-<-

LAH( ), (13)
->->
->->

!!!
<-<-

<-<-

->->
2
-OH

<-<-

->->

ester

or

<-<-

Protecting

DeProtecting

R-OTBDMS

R-OBn

R-OTHP

- xiii

diazotization
. Ben -> -> ->

Cumene

->

-> ->
,

-
Ben

--- ---->

() , o,p.
:
.

->

(benzoquinone)

(or )
. (benzoquinone) ->
- -

Fremy .
ether(R-O-R)

Williamson ether

: OH Na K alkoxide( ) 1 R-X( 1!!) .

: R-OH + -> +
ether :

+ (1) -> +

alkene :Williamson ether

6.
.

-> ->

/ ,

ehter

HBr or HI
. R-O-R' + -> RX + R'OH
HX/

-> RX + R'X
HX

ether
. Ben-O-

->

Ben-OH + /Br () -> Ben-Br(X)

-HBr-

-SN2 X(sp2 )-

carbo ether

- xiv t-butyl ether(

) Benzyl ether(Ben-OH) OH

ether(epoxide)
epoxide (10. Epoxidation)
. alkene +

->

(m-CPBA)

m-CPBA, MMPP
halohydrindp epoxide ()
ylide epoxide ()
expoxide

() - , -
) O 1, 2

: )

Grignard expoxide , epoxide , epoxide : pass~

Crown ether pass~

1. + NaSH

+ NaBr

->

SN2 .
2. +

-> +

sulfide
+ ->
Neighboring group participation

S ()

1. + ->
2. + ->

ans. 1 2 . S Good L.G

Bromonium
+HBr ->

->

Meso,[a]=0