Fye 30 A

O , M
O A
. ,
.
60
K E A A I O 1 : H M O A
.
: X Keq (> 103).
> 99,9%.
M (G): H G Keq
: G = RTlnKeq. E Keq > 1,
(G < 0). . T . H G (H)
(S) , G = H TS. H H
, S . M
( ).
M : H .
E Gibbs, G: T , . A
. G, .
E : A . O y
x (.. ).
: A ().
K : T G
( ), .
OYE TI YIKE EITHME

OPANIKH XHMEIA
A'
O ,
M O A
MANH TPATAKH
E K T X K
ATPA 2002

OYE TI YIKE EITHME

OPANIKH XHMEIA
A'
O , M O A
MANH TPATAKH
E T X
K

MIXAH OPANOOYO
T X K

EPIO KAPAKAKH
T X

EIPHNH EPIAH

MAA OIKONOMOY

...

TYPORAMA

/ 19972000
ISBN: 9605380897
K : YE 30/1
Copyright 2000

& , 26222 : (0610) 314094, 314206 : (0610) 317244
. 2121/1993,
.

K 1
H M O A
, ,
E ............................................................................................................... 13
1.1
A H
1.2
1.3
................................................................... 21
1.4
Y .................................................................................................................................... 23
1.4.1 Y sp3 ............................................................................................................ 23
1.4.2 Y sp2 ............................................................................................................ 25
1.4.3 Y sp ............................................................................................................... 26
1.5
1.6
E .............................................. 30
1.7
........................................ 31
1.8
1.9
E .......................................................................................................... 34
.................................................
17
...............................................................................................................................................
19
..................................................................................
............................................................................................................................
28
33
1.10 .................................................................................................................................. 35
1.11 O BrnstedLowry ............................................................... 36
1.11.1 O ........................................................................................................................... 36
1.11.2 .................................................... 39
1.12 O Lewis
..........................................................................................
1.13 O
..................................................................
1.14 T
1.15 M
40
42
.........................................................
44
....................................................................
46
1.16 I
....................................
48
1.17 M E
E .......................................................................... 53
...............................................
54
..............................................................................................................................................................
58
1.18
K 2
A K
, ,
E ............................................................................................................... 61
O , M O A
2.1
2.2
2.3
..........................................................................................................................
64
...................................................................................
65
...................................................................................................
66
2.3.1 O
........................................
68
2.3.2 O n .................................................................... 68
2.3.3 O ................... 68
.......................................................
70
...............................................................................
71
...................................................................................................
72
2.3.4 E
2.4
2.5
2.5.1 ............................................................................ 73
2.5.2 ........................................................................ 75
2.6
............................................................................................................................
2.6.1 O
2.7
...................................................................
81
.................................................................................... 82
...........................................................................................................
82
..................................................................................................................
83
2.8.1 K
2.8.2 K
2.9
77
T ........................................................................................................... 78
2.7.1 E
2.8
.....................................................................
77
............................ 85
2.10 cistrans
2.11
..............................................
87
........................................................................................................
89
2.12 A ......................................................................................................... 91
2.13 M
..................................................
91
2.13.1 E ........................................................................................................ 92
2.13.2 M ................................................................................ 93
2.13.3 ....................................................................... 95
.............................................................
96
.....................................................................................................................
96
2.14 A
2.14.1 X
2.14.2 B ....................................................................................................................... 98
...........................................................................................................................................................
101
............................................................................................................................. 104
EPIEXOMENA
K 3
, ,
E ............................................................................................................ 105
3.1
E .......................................................................................................................... 107
3.2
A R,S
3.3
O P ....................................................... 112
3.3.1 O ................................................................................................ 112
3.3.2 P ................................................................................................ 113
.................................................................................................................... 114
M ............................................................................................................................... 115
Fischer .................................................................................................... 117
.................................................................................................... 118
. H
............................................................................................................................ 119
3.8.1 X ............................................................................... 119
3.8.2 X (R)2.
A ............................................................................................ 120
3.4
3.5
3.6
3.7
3.8
..................................................................................
...........................................................................................................................................................
109
123
............................................................................................................................. 124
K 4
, ,
E ............................................................................................................ 125
4.1
4.2
4.3
4.4
4.5
4.6
........................................................................................................................ 127
O ................................................................................................. 127
...................................................................................................... 129
4.3.1 cistrans ............................................................... 129
4.3.2 X E Z .................... 130
..................................................................................................... 131
........................................................................................................ 132
A .................................................................. 133
4.6.1 K ................................................................................. 134
4.6.2 . K Markovnikov .......... 136
4.6.3 H2O () ....................................... 139
4.6.4 ........................................................................................... 140
O , M O A
4.6.5 ................................................................................ 141

4.6.6 E .................................... 143
4.6.7 ......................................................................................... 144
4.6.8 ................................................... 145
4.6.9 A ....................................................................... 146
4.6.10 O ....................................................................................... 147
4.7
A ..................................................................................... 149
...........................................................................................................................................................
151
............................................................................................................................. 152
K 5
, ,
E ............................................................................................................ 153
5.1
........................................................................
155
5.2
......................................................................
156
5.3
.......................................................................................................
158
5.4
A
5.4.1 A
........................................................................
159
.........................................................................................................................
159
.............................................
160
.........................................................................................
161
5.4.2
5.4.3 E
5.4.4 O
5.5
.........
162
O ............................................................................................................... 164
...........................................................................................................................................................
166
............................................................................................................................. 167
K 6
, ,
E ............................................................................................................ 169
171
6.1
6.2
............................................................................. 173
6.3
A .............................................. 173
6.4
K
.............................................................................. 176
6.5
A DielsAlder ................................................................................................... 178
.......................................................
...........................................................................................................................................................
182
EPIEXOMENA
K 7
, ,
E ............................................................................................................ 183
.................................................
185
..............................................................................
186
7.3
.............................................................................
187
7.4
A . M SN2 ...... 190

7.4.1 M ................................................................................................................. 190
7.4.2 X SN2
O .......................................................................... 191
7.4.3 X SN2
T ......................................................................... 192
7.4.4 X SN2
H ........................................................................................ 193
7.4.5 X SN2. O ................. 193
7.5
A . M SN1 ...... 196

7.5.1 M ................................................................................................................. 196
7.5.2 X SN1
O .......................................................................... 197
7.5.3 X SN1
T ......................................................................... 198
7.5.4 X SN1
H ........................................................................................ 198
7.5.5 X SN1
O ............................................................................................ 199
7.6
A . M E2 ...................................................... 200
7.6.1 M ................................................................................................................. 200
7.6.2 X E2 ....................... 201
7.7
A . M E1 ...................................................... 204
7.1
7.2
...........................................................................................................................................................
205
............................................................................................................................. 208
K 8
B A E
, ,
E ............................................................................................................ 209
O , M O A
10
8.1
8.2
8.3
8.4
8.5
8.6
O ................................................................. 211
...................................................................................................................... 212
K . O Hckel .............................. 214
A .
O ........................................................................................................................... 216
N, , ,
FriedelCrafts B ............................................................................................... 218
8.5.1 N .......................................................................................................................... 218
8.5.2 ............................................................................................................. 218
8.5.3 A .................................................................................................................. 219
8.5.4 A FriedelCrafts ............................................................................. 220
8.5.5 A FriedelCrafts ................................................................................ 221
E

....................
222
8.7
E ........................ 225
8.7.1 E ........................ 225
8.7.2 A ................. 227
8.7.3 A ............................................. 228
8.8
H
............................................................................... 229
8.8.1 H ...................... 230
8.8.2 H ....................... 231
8.9
..........................................................................................
232
8.10 A ................................................................................. 233

8.10.1 O ............................................................. 234
8.10.2 A ......................................................... 234
...........................................................................................................................................................
236
............................................................................................................................. 238
A
.......................................................................
239
A ...................................................................................................... 267

..........................................................
274
E
H O X
, X. B,
, . T , , ,
, , . E
, , ,
,
. E , , ,
.
M 19 ,
, (vis vitalis). ,
Whler 1828, , , ,
, .
O
NH4+ -OCN
K {{
{
H2N
NH2
O{{
K 20 , . O 12 . T, . O
, . T
, ,
12
O , M O A
(g)
. M
, . H
M B B
(.. , , ..).

( ),
, ,
.
H M O A

,
, .

, :

,
, ,
, Lewis Kekul,
,

,
,
,
,
,
/ Lewis
BrnstedLowry,
,
, , ,
,
,
14
G, H, S, G, , ,
.

A s, p d
Lewis
Kekul
Y sp, sp2 sp3
Van der Waals
E (+I I)
O Lewis
Ka
O
BrnstedLowry
O
H

E

Keq
M Gibbs, G
E , G

,

:
) ,
,
) ,
) ,
) ,
, .
, ,

, . E ,
,
,
.
T 1 :
1.1 A H
1.2
1.3
1.4 Y
1.5
1.6 E
1.7
1.8
1.9 E
1.10
1.11 O BrnstedLowry
1.12 O Lewis
1.13 O
1.14 T
15
16
1.15 M
1.16 I
1.17 M E E
1.18
A H
1.1 A H
, , ,
. O
, (Z). ,
(H) Z = 1 , (Ti) Z = 22 22 . O
, ,
. T
(A). , A = 12 Z =
6, 6 , 6 126=6 .
,
. M, , . , . T s, p, d
f, . H : s > p > d, p d s. T
(C, H, O, N)
s p , .
T s (1s, 2s, 3s .) ,
s
. T 1s 2s
3s, . T 2s 3s ,
, . ,
( )
. , 2p , , 3p, 4d
5d, .
17
18
T p (2p, 3p .) , ,
() px, py pz. H p (+), () . T
,
.
z
x
T s
T px
T pz
H ( ) , (1s, 2s, 2p,

3s, 3p, 3d .), Pauli
Hund. Pauli,
.
Hund, () ,
, . A , .
A
. (H, Z = 1) ,
1s. (C, Z = 6) 1s 2s, ,
2 , ,
Hund, 2p. H C , : 1s2, 2s2, 2p2.
1s
2s
2p
H C
(Ne, Z = 10) 1s, 2s, 2px, 2py 2pz (1s2, 2s2, 2p6). 1.1.
19
1.1
Y (H)
1s
(F)
1s2, 2s2, 2p5
A (C)
1s2, 2s2, 2p2
N (Na)
11
1s2, 2s2, 2p6, 3s1
(N)
1s2, 2s2, 2p3
(Si)
14
1s2, 2s2, 2p6, 3s2, 3p2
O (O)
1s2, 2s2, 2p4
A (Ar)
18
1s2, 2s2, 2p6, 3s2, 3p6
1.1
:
) Be,
) B,
) Li,
) Cl
1.2
Y , .
, . O
,
. I . , NaCl ,
Na+ (1s2, 2s2, 2p6) Cl (1s2, 2s2, 2p6, 3s2,
3p6),
.
I :
Na - e-
Na+
Cl + e-
Cl-
Na+ + Cl-
Na+ Cl-
O
. O .
+ B
B
O :{

20
O ,

(.. 2 8). O

, . , H ,
C , F Cl .
E
Lewis,
(). ,
( 1s),
( , 2s2 2p2) (
2s2 2p5). T . T H2O NH3 .
H +H

Lewis
H
H C H
H
H H
C + 4H
+ 3H
O + 2H
H
O
H
H N H
H
C + 4H +
H O H
H
H C F
H
H
N H
H
O Kekul,
(..
H2, HH).
H H
H H
Lewis
Kekul
H
H C H
H
H
H
H
H C H
H
H
C O
M
Lewis Kekul
21
,
, Kekul, C H. ,
, .
HH
H
C H
C C
H
H
C
C
H
H
C
H
H
H H
H H
H H H H H
H C C C C C H
H H H H H
Kekul
1.2
) Lewis, Kekul.
O
C
CH3
N
C
N
C H
C
C N
N
O
CH3
H3C
) Lewis.
C C H
1.3
O

(Molecular orbital, MO).
,
. K
A B AB
. , H2, -
22
1s ,
, .

H
T 1s, H
H H
M H2
T 1s, H
(MO), ( ) , ,
( ), ,
( ), , .
1s, ( ,
, H2), ,
. T . E
, ,
* .
H
A H-H (*)
A
1s H
A
1s H
H-H ()
s p, p p, s p . , HF
1s H 2p F.

T 1s, H
T 2p, F
M HF
H F
23
E, MO, p, , . K
*, .
A
* ()
+
A
p
A
p

()
O ,
p, .
1.3
HCl ClCl
.
1.4 Y
1.4.1 Y sp3
H (1s2, 2s2, 2p2) 2

1s 2s, 2 2p. M

, , 2s 2p
. , CH
. E C ,
, 2s 2p , CH, 2s C 1s H
2p C 1s H.
24
H
H C H
4 C-H
H CH . E 2s 2p , 2s
2p. , sp3.
1s
2s
2p
109o
1s
Y sp3
4 T sp3
Y
4 T sp3
T sp3 , . H ( ). , (CH4) sp3 1s . O

. O HCH 109.
109o
M CH4
Y sp3
H2O NH3, . (1s2, 2s2, 2p3)
25
2s 2p,
4 sp3, , , ,
. ,
N . ,
(1s2, 2s2, 2p4), sp3,
, O . sp3
(NH3) (H2O) ,
109.
M
107
105
M NH3
M H2O
1.4.2 Y sp2
T sp2 s p
. C s p
sp2 . T 120 ,
. T p
sp2 , .
1s
2p
2s
2p
1s
Y
3 T sp2
3 T sp2. To
2p

sp2
26
C=C, C=N C=O,

sp2. ,
H2C=CH2, , sp2
H, sp2
sp2 .
{p(
p-p)
120{
T p
= C
= H
M H2C=CH2
C
{pC-C, {
sp2- sp2
T sp
(K {
p. E {
{
1s
, { p {
C-H.)
p,
sp2 . T p , , . K , .
1.1
T BF3 , B (Z=5) sp2.
B sp2.
BF3.
1.4.3 Y sp
K s p
sp . H sp , 180. C p ,
, sp.
1s
27
2p
2s
2p
1s
2 T sp
Y
2 T sp
CC ()
CN (), C N sp. sp (HCCH). K
sp,
, 1s H sp . C p,
sp, . T p ,
. O pp,
). sp , (
sp, .
1.2
T BeCl2 , Be (Z=4)
sp. Be
sp. BeCl2.
1.4
T . E .
Be
28
1.5
A :
(A)
(CH3)3N
(B)
BeH2
H
C O
()
H
()
(E)
HCaCF
(T)
CF4
(Z)
HOF
1.5
H , AB, A B , , .. HH, CH3CH3, BrBr. ,

(CH3CH3),
, .
, .
, H3CCl, HF
., . . .
AB, B A,
A+B,
. (H3CCl) ,
, Cl , H 3C+Cl. O
29
, , (
). O
( ). 1.2
. O , H = 2,1.
1.2
2,1
4,0
2,5
Cl
3,0
3,0
Li
1,0
3,5
Cs
0,7

(.. CH),
0,52
(.. CO), 2 (.. LiF).
-
A+ :B I
1.6

:
) H3CLi,
) H3CMgCH3,
) H3COH,
) H3CNH2
30
1.6 E
K
, . H
. H AB ,
, (D). H , kcal/mol,
. T

. H D
. O , D, 1.3. E
, D.
, FF (D = 68 kcal/mol)
HF (D=136 kcal/mol) H3CF (D=108 kcal/mol).
A
A
B
+
O A-B
B
B
O A-B
A + B
+ B
:
A
AB
AB
1.3
E (D)
D
(kcal/mol)
D
(kcal/mol)
D
(kcal/mol)
HH
104
BrBr
46
(CH3)3CH
92
HF
136
II
36
CH3CH3
88
HCl
103
CH3H
104
CH3F
108
HI
88
CH3CH2H
98
CH3Cl
84
FF
68
CH3CH2CH2H
98
CH3Br
70
ClCl
58
(CH3)2CHH
95
CH3I
56
31
1.3, H2
H 104 kcal/mol, H2 H 104 kcal/mol.
H H
H
+ H
A 104 kcal/mol
H H
+ H
E 104 kcal/mol
H (
angstrom, ). ,
. , , . ,
(CI) CH3I (D=56
kcal/mol) (CF) CH3F (D=108 kcal/mol).
A
CH3 - Br
CH3 - I
CH3 - Cl
CH3 - F
1.7
K ,
(
1.3):
HCl,
II,
CH3Br,
CH3H.
1.7
Y , ,
Van der Waals. E
,
. H ,
.
+
32
,
, O, N F, , ..
OH, NH. A

. K H2O,
H+OH+,
(100 C). A,
H2S, H S, (.. = 60 C).
, , , .. O , .. (HOCH2CH2OH).
+
H O
+
H
O H
+
H +
+ H O
H +
N, H2O:
{{
H H +
O
- O
C C
H
H
H H
A, HOCH2CH2OH:
{
E ,
. A, ,
,
.
O . B
DNA
.
O Van der Waals,
. A ,
(). A
, C H -
33
, , ,
. , . T
. ,

().
-
H C H
H C H
H C H
H C H
H C H
H C H
H C H
H C H
H C H
H C H
H C H
H C H
-
van der Waals:

,
. T
{+ {-, {
{
1.3
T A B.
, . M
;
OH
A
OH
HO
OH
1.8
A , ,
, . O : = Qr,
Q r . E debye (D), 1 D =
3.3 1030 Cm. H ,
, . K
.
34
, , ,
( = 0).
, CO2 CF4 . A, (H2O, NH3) , ,
,
.
> 0
= 0
F
:
H
H
C
H
O C O
1.8
K .
O
O
A
O
Cl
O
B
1.9
() H BeF2
(>0).
() H BBr3 (=0).
1.9 E
E
, . , 1, CH3CH2CH2Cl. O CCl ,
+ C Cl. E-
35
,
C, , CCl.
CH3CH2CH2Cl : C+ C+
C+ Cl, + + +.
+
H H H H
H C C C C Cl
M
.....
......

H H H H
H H H H
H C C C C H
H H H H
Y (Cl) I

Y (H)

I (.. Cl),
. A, +I (.. Li),
.
1.4,
+I I. T
.
1.4
Y +I I
E I
F, Cl, Br, I, OH, CN, NO2,
CH=CH2, .
E +I
A, NH3+,
, .
1.10
M , Lewis Kekul. , , CH3COO. Kekul -
36
. E
; H . H

,
. O ).
. H (
H .
, .
O
CH3COO
O
CH3 C
CH3 C
K . H ( , ). E,
,
,
CO
C=O. ,
CO .
O
1/2
CH3 C
O 1/2
CH3 C
H

.
,
, .
, A B
.
Y :
{ { C-C {
{
{

.
A
O B R N S T E D L O W R Y
37
O ,
(
). ,
. , CC , .
K
) O . H ()
.
) O
,
. ,
, .
E, ( ) , .
1.10
() ;
)
H3C
O
C
OH
O
OH
H3C
)
-O
O-
OC
O
O-
1.11 O BrnstedLowry
1.11.1 O
O BrnstedLowry
(H+ H3O+), BrnstedLowry . T
, , , . , HA , A HA,
H3O+ ( H2O).
38
HA
H3O+
H2O
, HCl , H2O , Cl H3O+. T

(Cl) HCl H3O+
H2O.
+
HCl
H3O+
H2O
Cl-
O BrnstedLowry 1.5.
1.5
O BrnstedLowry
O
H2SO4
NaOH
HNO3
KOH
HCl
Ca(OH)2
CH3COOH
NH3 (NH4OH)
H , HA, , Keq, :
HA + H2O
O+
H3
+ A
Keq =
[H3O+] [A]
[HA] [H2O]

H2O ( 55,6 M), , Ka,
:
[H3O+] [A]
Ka = Keq [H2O] =
[HA]
O B R N S T E D L O W R Y
39
Ka , ..
HCl, Ka ~ 107.
, .. CH3COOH, Ka ~ 105, , Ka 1070, .. CH4 Ka ~ 1050.
( CH4 : CH4 CH3 + H+).
pKa,
Ka:
pKa = logKa
T ( Ka) pKa, ( Ka) pKa. HCl, pKa ~ 7,
CH3COOH pKa ~ 5, CH4, pKa ~ 50.
, . T ,

. , HCl ,
Cl ,
, Cl, . E, CH4
(pKa ~ 50), , , CH3,
.
1.11.2 o
A :
HA
O
H2O
B
H3O+

, ( ),
,
( pKa)
. , (OH)
, CH3COOH, , CH3COO H2O, H2O (pKa ~ 14) CH3COOH (pKa ~ 5).
K , OH CH3COO.
E, CH3 NH3,
, CH4, (pKa ~ 50),
40
NH3 (pKa ~ 32). A, (OH)

, H2O NH3.
CH3COOH
+ OH
CH3COO
pKa = 5
NH3
+
pKa = 32
NH3
NH2
CH3
NH2
OH
+ H2O
pKa = 14
+ CH4
pKa = 50
+ H2O
pKa = 14
pKa = 32
1
H (CH3OH) pKa ~ 16, (NH3) ~ 32 (HCN) ~ 9. :
CH3ONa+
NH3
CH3OH
+ Na+NH2
CH3ONa+
HCN
CH3OH
+ Na+CN
: E pKa CH3OH
pKa NH3, . A, , (CH3OH) pKa
(HCN).
1.12 O Lewis
B Lewis ,
, . O Lewis
. O
BrnstedLowry, ,
. ,
Lewis , , BrnstedLowry, . -
O L E W I S
41
BrnstedLowry, Lewis H2O,

CH3COOH ( Lewis), (H3O+).
CH3COOH
CH3COO
+ H2O
H3O+
O
Lewis
BrnstedLowry, (.. Mg2+),
3A , BF3, SnCl4,
AlCl3, B, Sn Al, ,
, : TiCl4, FeCl3, ZnCl2 .
F3B- +NH3
H 3N
B{
Lewis
BF3
F3B
O{
Lewis
NH3
M Lewis:
H ( Lewis) {
BF3 (
Lewis), {
{.
O , Lewis, . , , , Lewis
.
CH3OH
CH3OCH3
A{
A{
CH3NCH3
H
M {
Lewis
({
{
{
N O)
CH3
CH3
K{
CH3
A{
NH2
A{
CH3
C
OH
K {
42

Lewis. , ,
, ,
,
. ,
.
1.11
() H BeH2 Lewis.
() To F (pKa HF = 3,45),
CN (pKa HCN = 9,31).
() H CH3OCH3 H+,
.
1.13 O

.
O ,
(functional group) . H
, , . E
. ,

(OH)
. O
. E, CC, COC . H
43
(RH,
R , .. CH3CH2,
CH3CH2CH2, .). T
C H . 1.6
, .
1.6
O
O
RH
CH4
R2
R1
R3
C C
R1
R2
R6
CH3CH=CHCH3
CH3
R3
R5
CH3
R4
H3C C C H
R1 C C R2
RI, RBr, RCl, RF
I, Br, Cl, F
CH3CH2Br
ROH
OH
CH3CH2OH
R1OR2
CH3CH2OCH3
RNH2
NH2
CH3CH2NH2
R1NHR2
R1 N
C C
N H
NH
R2
RSH
R3
SH
(CH3)3N
CH3CH2SH
>
44
R1SR2
RM, RMgX
M =
S
M, MgX
CH3CH2SCH3
CH3Li, CH3MgI
O
R C H
CHO
CH3CH2CHO
O
C R2
O
C
R1
CH3COCH3
O
R C OH
COOH
O
R C OR1
O
C O
O
R C NH2
O
C N
O
R C X
O
C X
CH3COCl
R C N
C N
CH3CN
RNO2
NO2
CH3CH2NO2
R1SO2R2
SO2
CH3SO2CH3
CH3CH2COOH
CH3COOCH3
O
N
H
1.14 T
O : )
, ) , ) ) .
O ,
.
CH 3Cl NaOH,
OH NaOH Cl CH3Cl, CH3OH NaCl.
CH3Cl + NaOH
CH3OH + NaCl
45
O ,
. ,
H2C=CH2 HBr
, CH3CH2Br.
H2C=CH2 + HBr
CH3CH2Br
O ,
.
(CH3CH2OH) (H2C=CH2) H2O, H+.
H+
CH3CH2OH
H2C=CH2 + H2O
O ,
. 1
2 .
CH3CH2CH=CH2
H+
CH3CH=CHCH3
B-2
B-1
1.12
A , ,
.
+
() H2C=CH2
Pd
H2
() CH3CH2CH2Br + NaOH
()
COOH
() CH3CH2OH
NaOH
HBr
CH3CH3
CH3CH=CH2 + NaBr
H+
+ H2O
COOH
CH3CH2Br
H2O
46
1.15 M
. ,
, , , , . M ,
, .
, ,
,
( ). H ( ). A,
, .
Cl 2 Cl,
.
Cl - Cl
B
{
Cl
O {
O {
+ Cl
M {

, ,
. H . A,
, , .
(L). M
. T

(.. :NH3) -
47
(.. OH) .
H
. , 7 K CH3Br CH3+ Br SN1 .
A+
CH3Br
A+
B
+
B
CH3+ + Br
SN1
E
E
M ()

. ,
.
(.. OH),
(.. H2O), .
,
. , Lewis
Lewis.
A+
H
(O Lewis)
(B Lewis)
B
T B
AB
,

( ). 1,3 ,
6 K ( DielsAlder) .
M :
O

.
.
48
1.16 I
, (1.17
1.18),
,
, , , , . H (HBr) (H2C=CH2),
(CH3CH2Br). A 4 ,
,
,
( ),
.
HBr
H Br
H C C H
H
H
H
C C
H
A ()

O
. T . H (
)
Keq, :
A + B = +
:
Keq = []/[A] = [] [] / [A] [B]
H
. E Keq > 1, [] [] > [A] [B],
, . E
Keq < 1, , -
49
. , HBr, . 25 C,
Keq = 7,5 107. A Keq >>1, , .
E , . ,
(CH3COOH)
(CH3OH), (CH3COOCH3) H2O,
Keq ~ 2, . H Keq
1 mol CH3COOH 1 mol CH3OH
0,65 mol CH3COOCH3 0,65 mol H2O.
Keq ~ 2
CH3COOH + CH3OH
CH3COOCH3 + H2O
1
0,35
1
0,35
0
0,65
0
0,65
1
0,05
10
9,05
0
0,95
0
0,95
E , .. ,
,
CH3COOH . K ,
,
(CH3COOCH3).
T ;
M ,
.
K , ( )
. H Gibbs, G :
G = G G
50
G = 0,
. , A H B,
G = 0, A B , A
B 50%. H G , Keq,
, R
[1,987 cal/(Kmol)] T K:
G = RTlnKeq
Keq = eG/ RT
G , Keq >> 1, . , G 4 kcal/mol, Keq ~ 103,

> 99.99%. A
.
, Keq = 7,5 107.
H
, , H, , S,
:
G = H TS
H , H, , .
H = (I ) (I )
E H < 0,
( ). E H > 0, ' , ( ). K , H < 0, G < 0, ,
, TS G .
E ,
, ( H), ( H).
,
180 kcal/mol
190 kcal/mol, H = 10 kcal/mol, .
E
:
H = 180 kcal/mol
E
:
H = 190 kcal/mol
K :
H = 10 kcal/mol,

O , S,
. :
AB+
' , ,
. A
(S > 0). , :
A+B
, , S < 0.
O (H) (TS)
. E, ,
, , G ~ H.
H G ( )
.
, . M
, Keq
( ).
51
52
A B
A +
E : T .
O A AB.
H < 0.
E : T .
O AB A.
H > 0.
2
E, (D)
1.3, .
CH4
Cl2
CH3Cl + HCl
K H3CH (D = 104 kcal/mol)

ClCl (D = 58 kcal/mol) ,
H3CCl (D=84 kcal/mol) HCl (D=103 kcal/mol) . H 162 kcal/mol
187 kcal/mol. E, (H = 25 kcal/mol), .
1.13
K
, A B. M
D CH3CH2CH2Cl (82 kcal/mol) (CH3)2CHCl
(81 kcal/mol), 1.3,
.
M E E E
A
H H H
H C C C Cl + HCl
H H H
H C C C H
H H H
h
+ Cl2
H H H
H Cl H
H C C C H + HCl
H H H
B
1.17 M E E E
,
( ) . ,
,
.
, ,
. K
,
, . H ()
. H , ,
.
T
, Gibbs,
G. M G . O, . E G
, (
, ,
). A, G , . H , -
53
54
G . Y 10 C
, .
H .
, , , , ( )
( ), ().
AB + A + B. ,
A,
AB.
A-B +
A- +
M E
:
M
H G
,
. H G
,
.
1.18

,
, . O
,
. ,
HBr . T
H+ ( HBr) ,
55
. T , , . K (G),
(G).
, .
H
H
C
H
H Br
H C
H
+ H
C
+
H
H Br
Br
H C
H
HBr, , .
E
{
G2
+
CH3CH2
Br
G1
H2C= CH2 + HBr

G
CH3CH2Br
C H
H
56
E ( + HBr),
(),
. E, ,
.
,
, G ,
G1 , ( ),
G2 ,
(G = G1 G2 < 0).
E , , , ( ) . ,
. E , ,
,
(G1 > G2).
1.14
;
) M G = 25 kcal/mol G = 10 kcal/mol.
) M G = 30 kcal/mol G = +1 kcal/mol.
57
1.15
:
) E (A ) ;
) Y .
;
) A, B
;
1.16
25 C 1 mol
CH3Cl 1 mol H2O, CH3OH HCl.
CH3Cl
H2O
CH3OH
HCl
M 2 10% . T ;
>
58
) N , .
) H
. ,
( > 99,9%) .
) N . E
,
.
A T: H
. T s, p, d f.
H : , Pauli Hund. , C : 1s2, 2s2, 2p2.
I : O . , NaCl.
O : .
(MO). M Lewis
Kekul, , .
Y: A .
sp s p ( ,
.. BeCl2), o sp2 s p ( ,
.. BF3) sp3 s p ( , .. CH4).
: O ,
p.
: , .
E (D): E
. T
. K
. H D .
A : H . K .
van der Waals: A , .
:
( = Q r).
E : H , .
: M . O
. E .
O BrnstedLowry: E .
O Lewis: E , . K
Lewis .
O :
, pKa (
) .
:
.
T : Y, , . M
( ), ( ) (
).
Keq: H
59
A K
, , .
A
, :
C H , , ,
,
/ ,
,
Newman,

,
,

,
,
,
,
,
,
.
KEAAIO 2: A K
62
1/2/3
1/2/3/4
Newman
A van der Waals
E
gauche

cistrans
A Grignard
A Wurtz

. , . 1 2 , . , , : ) ()
, )
, )
.
T 2 :
2.1
2.2 E
2.3 O
2.4
2.5
2.6 K
2.7 T
2.8
2.9
2.10 cistrans
2.11
2.12 A
2.13 M
2.14 A
63
KEAAIO 2: A K
64
2.1
T . E . T
. , ,
(C1C4), C5C14
( ), C14C25 (),
25 (
).
T CC CH
. O
CH2+2. O CC
sp3 ,
CH sp3 C s H. O 109,
HCH CH4 CCH CH3CH3
.
, E 2.6 .
109{
CH4
A {
CH4 CH3CH3 {{
{
CH3CH3
T (n) .
, . O C H
. A
C , CH4. A
C 8 H , (C3H8).
C, . ,
C4H10: O -
65
(n) (). E
, ,
(C4H10), . E,
,
n , .
T
C4H10
CH3CHCH3
CH3CH2CH2CH3
n-Bo,
{{
CH3
I,
{{
M ,
. ,
C20H42 366.319 ,
C30H62 4.111.846.763 !
H .
, , , .
2.1
C5H12.
2.2 E
O (1o), (2o), (3o) (4o) ,

. C (1), , (
), (4).
KEAAIO 2: A K
66
H
(1).
R C H
E
H
R
(2o).
R C H
E
H
R
T (3).
R C H
R
T (4).
R C R
E
R
K , (1),
(2) (3),
. ,
C, (2) . E
.
H
R C H
H

R
R C H
H

R
R C H
R
T
2.2
C H 1, 2, 3 4.
2.3 O
. H
IUPAC (International Union of Pure and Applied Chemistry)
: , .
T
. . E
67
C, , C, ,
. E , ,
C, : , , ,
. H
(.. Cl, COOH, OH .). T, .
K M K
2.1 .
2.1
H
O
C=C
CC
OH
CHO
C=O
COOH
H .
, 31.
O F
3
K -
F
CH3CH2COOH
K
3 C
CH3CH2CH2CHCH2CH2OH
6
K 6 C
31
KEAAIO 2: A K
68
2.3.1 O
T ,
. ,
n,
n.
n-B
n-O
2.3.2 O n
H ,
, R, RH. O n , . ,
, , n n .
H
CH3CH2CH3
CH3CH2CH2
n-
A
H
CH3CH2CH2CH2CH2CH2CH2CH3
CH3CH2CH2CH2CH2CH2CH2CH2
n
2.3.3 O
T , :
) B
. ,

, (
) C.
O{ { {
{{,
C
69
A ,
. ,
.
O
(,,,)
OXI

(,,)
) H C , . A ,
. O
. A
, .
) O ,
, , . E ,
. E,
, , , .
T . ,
52,2
47,7, .
,
.

7
8
5A2,2
2
3
4A7,7
) E ,
. O ,
.
KEAAIO 2: A K
70
, 4
, C
(), (1). ,
4(1)2,3,5.
2
4
5
4(1M)2,3,5
2.3.4 E
,
IUPAC. , , .
H
H3C C
CH3
H
H3CH2C C
CH3
(iPr)
(secBu)
CH3
H3C C OH
CH3
4I
tertB
CH3
H3C C
CH3
CH3
H3C C CH2
CH3
tert (tertBu)
CH3
H3C C CH2Cl
CH3
N
A O A
) B . E
, .
) A ,
.
) O , .
71
) H
, .
2.3
O :
2.4
O . B
.
) 5,5,6T
) 4,43
2.4
T n C1C4 , C5 C17 ,
(C18 ) . T
n C.
A
van der Waals, ( n E 1.7). O van der
Waals .
, , .
T
,
,
. , n (..) 36 C,
2,2 10 C.
KEAAIO 2: A K
72
n, .. = 36 C
CH3-CH2-CH2-CH2-CH3
2,2, .. = 10 oC
CH3
H3C C CH3
CH3
T n
2,2,
van der Waals.
2.5
M ,
, . M .
H , . T . E ,
: , .
,
CC . E,
, CH, . T . M ,
Newman, CC ,
,
. O
,
.
R3
R6
73
R6 R4
R1 C
C
R5
R2
R1
R4
R3
R2
R2
R6
R6 R4
R3 C
C
R5
R1
R3
R4
R2
R5
R1
R5

(A B). H B

CC A.
,

.
M A
B Newman.
O
CC,

,

.
Newman
A , .
2.5.1
H , Newman . H
Newman, ( ) CH
, .
60, CH
( ). , CH 0,
.
60 . H ,
CH,
( ). H . A, , . M . O

.
KEAAIO 2: A K
74
H
H
C
H
H
HH C
H
C
H
H
H
C
H-C-H 60o
H
H
T {

C-H
H
H
H H
{
H
H
H
H
H
d:
O C-H
60{.
H { {
,
{
{
HH
H
H
M {
{{
.
E d:
O {C-H
,
{.
T CC .
4 kcal/mol
H
H
H
H
H H
H H
H
H
H
H
H
H
H H
H
60
120
H
H
H H
H
H H
H
180
H
H
H
H
240
H
H
H
H H
H
H H
H
300
360
H
H
H
0, 120, 240{
E
H
60, 180, 300{
75
T
. H
,
CH , .
2.5.2
K CC , () .
C2C3
Newman :
{
T {
CH3
H 3C H
H
CH3
d:
H {
. {
.
CH3
H
H
CH
H 3
E :
T {
CH3-H
H-H.
H3C CH3
CH3
H
H
H
H
H
gauche:
A ,
{
CH3-CH3.
H

, ,
180. M C2C3 60,
CH3H
HH. H . M 60,
60. H
gauche
, (
). H gauche
E
{. E{

CH3-CH3,
H-H.
KEAAIO 2: A K
76
. H
,
, , (
van der Waals), :
A van der Waals
CH3
CH3
CH3
H
H

gauche ,
{
H
H
K ,
0 . E ' , gauche, HH, . H
.
gauche .
2.5
) O
.
) H gauche 1,2 (ClCH2CH2Cl)

.
) H

.
) T
2,2
CC ,
.
77
2.6 K
T .
C (.., ). K , , , .
HO
N
,

X
T ,

2.6.1 O
O , , .
:
) E
,
. . :
CH2CH2CH2CH2CH2CH3
CH2CH2CH2CH2CH2CH3
O 1
.
O
1.
KEAAIO 2: A K
78
) O ,
. :
CH2CH2CH2CH3
CH2CH2CH2CH3
3
4
1
3
CH2CH3
Cl
H3C
1
CH2CH3
OXI 15
O: 13
Br
1
CH2CH2CH3
CH3
1B2,4
12
2.6
O :
H3C
F
A
Br
CH3
B
2.7 T
A sp3
109,
( 108) ( 120) .
,
CCC, 109.
, CCC 60
109 49. M
, (.. )
. E ;
79
C-C-C {. A
{ . T
.
60{
K{{
90{
108{
120{
K{{
K{{
K{{
H
,
CO2 H2O ( E 2.12). H , .
, A
B , A
B. K
A B , ,
A B .
CxH2x + 3x/2 O2
A
x CO2 + x H2O +
K CxH2x . E

.
K CxH2x .
E
H1
H
H2
A (H1)
B (H2).
(xCO2 + xH2O)
( ),
, ( CH2),
KEAAIO 2: A K
80
147,5 kcal/mol. ,
, 147.5 kcal/mol, CH2 . , , = 3, 147.5 3 kcal/mol. T
2.2.
2.2
K, C3
K, C4
K, C5
K, C6
K, C7
K, C12
K, C15
E

kcal/mol CH2
T
kcal/mol*
166,6
164,0
158,7
157,4
158,3
157,6
157,5
27,6
26,4
6,5
0
6,3
2,4
1,5
* O ,
CH2 157,4 kcal/mol
CH2 .
, : T = (158,7157,4) 5 = 6,5 kcal/mol.
T , , ,
. E,
, .. .
,
CCC
109; E,
, ,
CCC 108 120; H
. A,
,
. E , ,
.
.
81
, , .
2.7.1 E
H : , .
) H CCC
109.
109, . ,
,
CCC ( 49) 109.

CCC 109.
60
) T ()
(),
CH .
H
H
E
CH.
HH
H
H
) H ,
, ,
,
gauche 2.5.2.
{
CH3
{
CH3
CH3
H
H
O

(C7C11), ,
E 2.9.
KEAAIO 2: A K
82
2.8

, .
.
2.8.1 K
T CCC
60. E sp3 , CCC . , sp3 ,
, CC. , CC CC
. (O , . H
).
109o
K CC .
H sp3

T CC
H 27,6 kcal/mol ( 2.2).

O , ,
, CH
. CH.
H
T ,
CH
.
H
H
83
2.8.2 K
2.2, . K ,
CH
,
. H
( ), , ,
, .. C1 C4 ,
, . ,
.
, C2, C3, C5 C6 ,
C1 C4. H .
6
4
2
H
H
E {{
4
2
:
M C1 C4
{
. {
{
,

C-H.
H CH , Newman:
CH
H
H
CH2
CH2
H
H
H
H
Newman .
C2 C3 C5 C6.
CH .
, (axial, a) (equatorial, e). T , , -
KEAAIO 2: A K
84
. T
. T (
) . ,

C2, C4 C6 C1, C3 C5.
. O C2, C4
C6 , C1, C3 C5 .
a
a

e
4
5
2
e
3
2
6
a
a
a
a
e
e
T
. H .
M C4

a
a
e
e
a
a
e
a
a
e a
a
e
a
a e
e
a
A .
T (a)
(e)
,
.
M C1

H
,

( C1 C4). A
.
85
2.7
:
H3C
H
CH3
H
H
H
E {{
2.9
, ,
(a) (e). , . M
.
(a)
CH3
H (e)
A
CH3 (e)
(a)
H
I
O , . O ( )
, (G)
E 1.16:
K = e(G/RT) K = []/[]
,

. , ,
G=1,7 kcal/mol, ,
(25 C)
K=21. , 95,5% 4,5% , K = 95,5/4,5 = 21.
KEAAIO 2: A K
86
CH3
H
K
CH3
K = 95,5/4,5 = 21
H
4,5%
95,5%
H
,
1,3 C1
C3 C5. , .

H
5
CH3
H
1
H
5
H
H
CH3
A :
1,3
CH3
H C3 C5.
I :
1,3
CH3
H C3 C5.
2.3

Y (Y)
F
Br
OH
CN
CH3
CH(CH3)2
C(CH3)3

1,3
H Y, kcal/mol
H
5
Y
H
0,25
0,5
1,0
0,2
1,8
2,2
5,4
T 1,3 . , 1,3 ,
. 2.3 -
C I S T R A N S
87
1,3
. , tert, tert . H
tert 99,99/0,01, G=5,4 kcal/mol ( 2.3), K>104.
CH3
H3C C CH3
H
<0,01%
CH3
C CH3
H CH3
K > 104
>99,99%
2.1
1,1 ,
. M 2.3,
;
F
Br
CH3
CH3
C
H3C CH3
2.10 cistrans
,
. T
, . ,
1,2. T
(cis )
(trans ). ,
1,3 .
KEAAIO 2: A K
88
Y cis
H3C
Y trans
H3C
CH3
CH3
trans1,2
cis1,2
H3C
H3C
CH3
cis1,3
CH3
trans1,3
H cistrans
4 K.
2.8
) H /
(C6H11CN)
/
) O :
) 1,1,
A B.
A
CH3
CH3
H3CH2CH2C
H
CH3
CH3
CH3 H3CH2C
H
CH2CH3
) G>0.
OH
H
Go > 0
OH
H
89
2.11
O :
) Y (
4.6.1). E C=C
H2, Pt Pd Ni.
Pt Pd Ni

CH2
H2
CH22
H2
CH2+2
Pt Pd Ni
H2
CH2
Pd
) A . H
( Grignard, RMgX). T Grignard (RX) Mg .
RX +
Mg
RMgX
RMgX
A Grignard
RH
H2O
Br +
Mg(OH)X
Mg
MgBr
H2O
) . (RLi) (R'X), R'R. O CLi Li .

RX
2 Li
RLi
R'X
Br
LiX
LiX
2 Li
RLi
R R'
Li
CH3I
LiI
CH3
KEAAIO 2: A K
90
M Wurtz,

Na,
, . E Na , .
RX
2 Na
Br
- 2NaX
A Wurtz.

R R
2 Na
2.9
.
CH3
H2
CH3CH2CH2Br +
Na
Br
Pd
Br
CH3CH2Br +
2 Li
2.10
: ) , ) D2O B,
.
( D H).
Cl
Mg
D2O
2.11
2,3. ) . ) .
91
2.12 A
T , ( parun affinis ). O
.
) K
H CO2 H2O. E ,
( , .) . CH2+2 :
CH2+2
CO2
(3+1/2) O2
(+1) H2O +
) A
T (Cl2, Br2 .) ( h)
(>250 C), .
C H
+ X2
h T>250 oC
C X
+ HX
X =
, , , . , , , , , ( Cl2 , .).
Cl2
Cl2
CH4
CH3Cl
h
Cl2
CH2Cl2
CHCl3
Cl2
CCl4
2.13 M
H ( , E
1.15). O ,
, .
-
KEAAIO 2: A K
92
, .
2.13.1 E
T ;
O , . T , .. Cl, H.
O : ) , ,
, )
,
. :
Cl
H
+H C H
H
H
H C
H
Cl
Cl - Cl
Cl
+ HCl
A (CH4)
(CH3)
(HCl)

O sp2. A , , CH3. K CH4 H, CH3. O sp3 ( ) sp2 ( ). ,
HCH 120, p ,
.
T p

, C-H
Y
sp3,
H
H
H
H
H
Y sp2. O C
H .
93

. H
> > > CH3. :
CH3
H3C C
CH3
CH3
H3C C
H
H
H3C C
H
H
H C
H
M
1.3 (E 1.6) (D) (1) , (2) (3). ,

95 kcal/mol, 104
kcal/mol. E,
9 kcal/mol . H , .
2.13.2 M
A
) .
ClCl
Cl (. 1.15).
h
Cl
2 Cl
Cl
:
O Cl Cl
) . M ,
HCl (CH3).
H
H
Cl
C
H
Cl +
E {
A {
CH3 Lewis
CH3
KEAAIO 2: A K
94
H Cl2, (CH3Cl) . H
Cl o. T ,

. , . E,

(Cl).
Cl
+
+
CH3
+
Cl
CH3
CH4
+ HCl
CH3Cl + Cl
Cl2
CH3
CH4
+ HCl
...
) T. T ,
, ( , E 1.16). T Cl2 ,
CH3CH3 CH3, CH3Cl
Cl CH3. , . O ,
.
Cl
Cl
Cl2
CH3
+ CH3
H3C CH3
CH3
H3C Cl
Cl
T Cl,
95. T
, , CH3 (1 ). T ,
,
.
95
A
Cl{
+{
CH4
HCl{
+{
CH3
CH3 + Cl2
CH3Cl + Cl
2.13.3.
H
: F2 > Cl2 > Br2 > I2. H
. O

Gibbs (G) ( ),
.
, ,
G
= 4 kcal/mol, , G = 18 kcal/mol.
Cl
CH4
CH3
+ HCl
G = 4 kcal/mol
Br
CH4
CH3
+ HBr
G = 18 kcal/mol
2.12
, ; (Y:
1.3).
KEAAIO 2: A K
96
2.13
K :
CH2
CH3
CH3
2.14 A
H
. .
2.14.1 X
K , 1 2 43/57. , 75/25 ( 6/2), , 1, , 2.

CH3CH2CH3
1
1
6 2
2 1
H H H
H C C C H 1
H H H
1
2 1
Cl2
h
H H H
H C C C Cl
H H H
H Cl H
H C C C H
H H H
43%
57%
75%
25%
E, 2
22 21 36/64,
10/90, 2 ,
21,
, 22.
CH3
H3C C CH3
H
97
H 1
H
C H H 1
1 H
1 H C C C H 1
H 1
1 H
H
1
Cl2
h
CH3
CH3
H3C C CH2Cl + H3C C CH3
H
Cl
64%
36%
90%
10%
,
; , : )
(X)
(HX) (R) )

> > . A 1 2, , .
,
Cl2
CH3CHCH3
Cl
+ CH3CH2CH3
-HCl
Cl
H3C C CH3
H
2-X
CH3CH2CH2
,
Cl2
CH3CH2CH2Cl
1X
A , 1. A
, ,
2. H (G)

. E, 1/2 = 75/25, 2
(57%).
KEAAIO 2: A K
98
2, 22 36%, (10%), , .
T ,
Cl
CH3
H3C C
CH3
CH3
-HCl
+ H3C C CH3
H
Cl2
CH3
H3C C CH2
H
H3C
H3C C Cl
H3C
2M2
Cl2
H3C
H3C C CH2Cl
H
2M1
2.14.2 B
,
( 2.13.3)
.
K 2
1 92/8, 2, 22
>99% 12 (<1%).
CH3CH2CH3
Br2
h
CH3CH2CH2Br
8%
Br
+ H3C C CH3
H
92 %
CH3
H3C C CH3
H
Br2
h
CH3
H3C C CH2Br
H
<1 %
CH3
+ H3C C CH3
Br
>99 %
H ,
, , . K , CH , -
99
. E, TS1 , TS2
.
E , TS1 TS2 .
XPIH{
Cl{
Cl{
H{
CH{3CH{
{
2CH{
{
3{ +{ Cl{
{ H{3{
H{3{C C C{
H{
+{
H{ H{
H{3C
C C{
{ H{
{
H{ H{
TS{1{
M d
O { {H-Cl { { { { { {
{{ {
{
{C { { {{{
. H {
TS{1{ T{S{2{ .{
TS{2{
TS{2{
E{
TS{1{
A, , . O CH ,
. A , . , TS3 TS4 ,
TS3 ( )
TS4 ( ). H

, ,
.
KEAAIO 2: A K
100
BPMIH{
H{
CH{3CH{
{
2{CH{3{ +{ Br{
Br{
Br{
H{
H{3C
C C{
{ H{3{
{
H{
+{
H{
H{3{C C C{
{ H{
H{ H{
TS{3{
TS{4{
M d.{
O { { H-Br { { { { { {{
{C { { { { {
.{ H { { { { { {
TS{3{ T{S{4{ {
TS{1{ T{S{2.{{
TS{4{
E{
TS{3{
A ,
: ,
.
2.14
K 1,4 . A .
;
) E A, 1 ,
(2 3).
) E B,
.
) E , , .
Br
H3C
CH2Br
A
Br
CH3
H 3C
B
H3C
CH3
101
2.15
) H F2
CH3F
Cl2
CH3Cl. E,
.
) H

.
) K
2,2,4
4 .
A: H . .
(n)
( ).
: I ,
. .. n 2.
, , :
X .
,
.
, : X , . T
.
O :
.
102
KEAAIO 2: A K
:
CC.
Newman: T
C
CC.
:
Newman 60.
E :
Newman 0, .
: H
.
gauche:
60,
.
: T

van der Waals .
: T ,
CCC 109.
K : sp3
.
: (C1 C4) . H
,
CH .
I (e): T
.
A (a): T
.
A :
. K ,
.
: . H , 1,3 C3 C5.
: ) K , ) Y Grignard ) , .. Wurtz.
A : ) K O2 ) ,
( ).
: H > > > .
E : ) : F2
> Cl2 > Br2 > I2. ) K ,

. ) H
, ,
.
103
KEAAIO 2: A K
104
K 2
1. :
2. K
:
CH4
CH3CH2CH2CH3
(CH3)3CH
3. .
CH3
H3C C H
CH3
CH3
CH3CH2CH3
4. T Wurtz Na .
, 1,3 .
:
5.
:
(CH3)3CH
+ Br2
Br2
C4H9Br
C5H9Br
(A)
Li
(A)
,
.

, :
, ,

R S,
,
Fischer,
.
E R, S
K ChanIngoldPrelog
E []D
Fischer

. M
KEAAIO 3:
106
,
. H

, .
,
,
, (
E 2.1). , n .
, ,
,
( E
2.10). A 3 , ,
) , ) ) . K 3 , .
, . E
, sp3
!
T 3 :
3.1 E
3.2 A R, S
3.3 O P
3.4
3.5 M
3.6 Fischer
3.7
3.8 . H
107
3.1 E
,
sp3 . O
, ) , )

)
.

,
:
H
H
C
H
H C
H
H
C-H
.
C-H
.
A . M
(CAB) .
, . A , .
E
C
B
C
B
CAB.

.
T .
,
, ,
. (chiral).
KEAAIO 3:
108
X .
,
. CAB

. , CAB .
E
BC
X CAB
B
A C
CAB

.
M CB
B
C
CB

.
A, C , .. CAA,
. A . :
A
C
A
C
A
O
,
,
C.
A R, S
109
. , . E, (.. ), . T

, E 3.3.
3.1
Y :
H
H
OH
H
K
H3CO
H
H H
N
S
N
O
V
N
O
CH3
CH3
COOH
3.2 A R, S
O
CAB Cahn, Ingold Prelog. T ,
() . A,
. E
, S, ,
, R.

R.
,

S.
KEAAIO 3:
110
,
() , ,
, R,
S.
H

. E
()
R.
.
, .
O
:
) M
C . , : Br (Z = 35) > Cl (Z = 17) > O (Z = 8) > N (Z = 7) >
C (Z = 6) > D (Z = 2) > H (Z = 1).
) E C, . E ,
, . , CH2CH3
CH3, CH3 C H, CH2CH3
C. , CH2CH2F CH2CH2CH2Br.
) O .
, CH=CH2 CH2CH3,
C=O COH.
:
A R, S
111
: Cl>F>CH3>H.
E

, R.
Cl
CH3
CH3
C
: F>CH2OH>CH2CH2Cl>CH3.
E

, S.
CH2OH
CH2CH2Cl
, .. R, (S) . E , , :
A
H
C
HO
CH3
COOH
OH
HO
H
HO
COOH
CH3
COOH
CH3
E. B

CH3 COOH A.
T.
CH3
COOH, H OH
.
CH3
COOH
3.2
X A,
.
H
A
Br
CH3
C
HO
CH3
CN
CH3
C
NC
Br
C CH3
COOH
H3C
CH3
COOH
Br
H
OH
CN
CH3
C
Br
H
C
Br
CN
H
CH3
CN
CN
CH3
C
Br
CH3
H
KEAAIO 3:
112
3.3
C R S.
H
H H
N
S
O
HO
Cl
CH3
N
O
CH3
CH3
COOH
3.3 O P
3.3.1 O

( R
S), . E , . H
, ,
, .
A{
{
.
{
{{
K{
{
,
{
H , , .
,
, [],
, , ,
C ( gr/ml), l ( dm). D (589 nm)
25 C (: []D25).
[] =
C l
O P
113
K [] . H []
. (R S) [] . ! R
S []. R
[]. E R , S
. , S []D25 = +3,82, R []D25 = 3,82.
H
(S)-
[]D = +3,82o
C
HO
H
HOOC C
OH
H3C
COOH
CH3
(R)-
[]D = -3,82o
3.3.2 P
P
, 50% R + 50% S. E .
E , [],
(.. + ), ( ) [] (+=0).
H
H
C
HO
COOH
CH3
(S)-
C
HO
CH3
COOH
(R)-
P
50% (S) + 50% (R)
[]D = 0
3.4
H R A []D = +80. A []D = 40.
R S;
KEAAIO 3:
114
3.4
, . A , (C*). C* , R S. E, C*
, R S , R1R2,
R1S2, S1R2 S1S2, 1 2
C1 C2. E ,
2. ,
3 , 23
= 8 . H , , 8 C, 28 = 256
.
.
*
*
*
*
HO

C; A 23.
, 2S,3R,
2R,3R, 2S,3S 2R,3S. T 2 3 2 3.
T 2--3-
H3C
F
S
H3C
F
CH3 R
H3C
CH3 S
CH3 R
H3C
H
Cl
2S,3R
H
Cl
2R,3R
Cl
2S,3S
CH3 S
Cl
2R,3S
115
E , 2S,3R 2R,3S
, . T 2R,3R 2S,3S. , 2S,3R
2R,3R 2S,3S, . T 2S,3R
2R,3R, .
F
F
H3C
H3C
H3C
H
Cl
CH3
H
Cl
RS
:
-
.
RR
, 2 ,
2/2 . 23 22 = 4 22/2=2 .
, .
3.5
T A B, .
COOH
H
CH3
H3C
COOH
H
COOH
H
CH3
H3C
Br
CH3
Br
A
COOH
H
H3C
H3C
Br
CH3
CH3
CH3
Br
B
3.5 M
A C,
, , {HOOCCH(OH)CH(OH)COOH}.
A ,
2R,3S/2S,3R,
(), .
KEAAIO 3:
116
COOH
H
OH
HO
H
COOH
HO
COOH
H
OH
COOH
2S,3S
2R,3R
COOH
OH
COOH
H
HO
HO
OH
COOH
H
COOH
2S,3R
2R,3S
, 2R,3S 180, 2S,3R. A, 2R,3R/2S,3S

, . M
2R,3R 180 2S,3S.
T 2R,3S 2S,3R .
COOH
H
OH
COOH
HO
H
T 2R,3R 2S,3S EN .
COOH
H
OH
180
OH
COOH
2R,3S
COOH
OH
HO
H
COOH
HO
2S,3R
180
H
COOH
HO
H
COOH
EN 2S,3S
2R,3R
2R,3R.
T , , 2R,3S , (meso). T
. E 3.1 ,
.
H
COOH
OH
E
OH
COOH
H ,
[]=0. ,
F I S C H E R
117
, , ,
.
3.6
H , ,
(). E.
Br
Br
3.7
) T S A
[]D = +35. 45% S
55% R []D.
) T cis1,2
.
) T
, []D.
3.6 Fischer

Fischer.
Fischer,
, . ,
,
, :
KEAAIO 3:
118
, (2S,3R)
Fischer :
HO
COOH
H
HO
HO
2S,3R
HO
H
COOH
COOH
H
H
COOH
M
(2S,3R)
Fischer.
3.8

R S. D, Z=2
H H
CH3
H
CH2Cl
OH
H3C
D
Cl OH
3.7
, . O , . E, , .
IOMEPH:
E {
{ {
{{ {
{
{ {
E{
EN
{
. H
119
T ,
:
)
, ..
)
, ..
CH3CH2OH
)
, ..
CH3OCH3
OH
OH
T , .
. T
. T ,
.
COOH
H
OH
(S)
H
C
HOOC
H
CH3
OH
H3C
HO
(R)
E:
.
COOH
OH
(2R,3S)
(2R,3R)
HO
COOH
H
COOH
OH
COOH
:
.
3.8 . H

,
. ,

(R)2. M E 2.13 2.14
.
3.8.1. X
K -
KEAAIO 3:
120
, 1 2.
1 ,
2 .
2; O
2 ,
Cl2 , .
CH3CH2CH2CH3
Cl
H3CH2C
-HCl
C
H
CH3
H
+
H3CH2CH2C C
Cl2 - Cl
Cl2 - Cl

H
H3CH2C C CH3
Cl
CH3CH2CH2CH2Cl
1-X
2-X
H (
sp2, 2.13.1),
Cl2 . E, (R)2
(S)2 5050%. ,
.
H Cl2

.
()
()
C
H
Cl
H3C
CH3
50%

()
Cl2
H3CH2C
(R)
CH3
H
C
CH2CH3
C
H3C
CH2CH3
E . ,
H
, CH3
-CH2CH3 .

()
C Cl
H3CH2C
(S)
50%
3.8.2 X (R)2. A
K (R)2,
. H
121
(R),
. T 1,2, 2,2, 2,3 1,3. E , 2,3 .
2,3;
(R)
H3CH2C
Cl
CH3
H
Cl2 h

H3CH2C
Cl
CH2Cl
H
H3CH2C
Cl
CH3
Cl
H
+
H3C
Cl
CH3
Cl
ClH2CH2C
Cl
CH3
H
A Cl2
2,3.
,
. H Cl2 (), (H), (), (Cl). K , o Cl
H. H () R,S ,
() R,R.
H Cl2

(),
.
Cl2
()
()
H
C C CH3
H3C
Cl H
(R)

()
H
CH3
Cl
H
Cl
H3C
CH3
C
H C Cl
H3C
(R,S)

H
H3C

()
Cl
H
Cl
H3C
(R,R)
KEAAIO 3:
122
H
, , , . K ,

. K (R)2 2,3,
S R.
3.9
) K

2.
) K
n
.
) K
(R)2,
22
[]D = 0.
) K
(R)2,
21
(S).
) T 1 2,

,
.
YNOH
E: .
X : .
A :
, CAB. E C
.
R, S: X , . H
KahnIngoldPrelog.
E []: X .
T [], . T [] R S. M R S.
P : 50% R + 50% S. H []=0.
: .
M: C
.
Fischer: T . O
.
A :
5050%. H
, .
123
KEAAIO 3:
124
K 3
1. X A, , .
A
H
F H
OH
CH3
H3C
CH3
H
F
H
F
CH3
F H
OH
H
Cl
Cl
CH3
H3C
H
Cl
H
D
Cl
H
Cl
H3C
CH3
Cl
2. R S
( C).
OH
O
HO
H
HO
B C
H
CH2OH
3. ( ) (S)2; .

, :
,
E Z,
,
,
,
,

,
Markovnikov
,
HX
,
,
,
HX
,

,

KMnO4 ,
.
KEAAIO 4: A
126

cistrans
E, Z
K Markovnikov
K
A
I
Y
cis trans

.
E 4.6 3 . T 4 , ,
. , , , .,
. T, , , , , , ..
T 4 :
4.1
4.2 O
4.3
4.4
4.5
4.6 A
4.7 A
127
4.1
T C=C. E
, .. , , .. ,
..
H
H
H
CH3
C C
H3C
CH3
T CH2. O
sp2 (
1.4.2 H 2C=CH2). K ,
, 120. K
p ,
. T p . , p
. H (E 4.6)
p .
M H2C=CH2
120
4.2 O
T , . Y :
) ,
.
O ,

C.
KEAAIO 4: A
128
) A ,
. E
,
.
4
1
2
5
7
OXI
O 4--4-
1
3
5--4-
) O (
2.3.2). , , ,
. C1 C2 .
2
3
1
2
5
2-M-1,3-
1,6-
. ,
, , (H2C=CH2) . E, (E 4.1) IUPAC, .
4.1
O . B
.
2-M-1-
()
2,5-E
1-M-2-
()
()
129
4.3
E 2 K CC
. , (E 2.5). , ,
. C=C , .
4.3.1 cistrans
A () , .. 2. Y . M ( )
cis
trans.
H3C
2-B
H
C C
C C
H3CHC CHCH3
H3C
CH3
CH3
cis
trans
T cistrans ,
. E

, .
H , . , ABC=CAB, ABC=CA, ABC=CB
ABC=C,
, ABC=CBB ABC=C.
A
ABC=C
ABC=C
C C
C C
C C
KEAAIO 4: A
130
4.3.2 X E Z
O cistrans
.
E Z. E Z, CahnIngoldPrelog,
E 3.2. E ,
Z, , , E. K ,
E Z. , cis 2 (Z)2.
O
(F { CH3)

,
{E.
Cl
CH3
OCH3
H3CO
O
(Cl { F),
{
,

{Z.
Br
{
Cl
H
{
(E)
H3C
H
(Z)
4.2
E Z. D, Z=2.
CD3
CH3
Cl
131
4.4
H : ) ) .
) B
, . A
. X
, (E 2.13) (E 4.6),
. , , .
H
H3C
H
C C
H3C
C C
CH3
C C
H3C
CH3
H3C
H3C
C C
CH3
CH3
)
T
. , cis2
trans2, trans, cis , trans. ,
, .
H H
H
cis
H
H
H
C C
H H
H
H
trans
C C
H
H
cis
E
trans
KEAAIO 4: A
132
4.1
K cis trans2 (C4H8 + 2O2 4CO2 + 4H2O). 2 ,
;
4.3
) T trans2
cis2 0,95 kcal/mol.
T trans2,2,5,53
cis ,
0,95 kcal/mol.
) T
.
) T :
H3C
H3C
CH2CH3
H3CH2C
CH3
H3CH2C
CH3
CH2CH3
4.5
O :
) A . K , (.. KOH)
, :
H X
R C C H
H H
R-CH2-CH2-X
R
+
H
C C
KOH
H
+ KX + H2O
KOH
Br
133
) A
(H+). H2O
, . ,
OH H .
H OH
R C C H
H H
R-CH2-CH2-OH
OH
H+
H+
H
C C
+ H2O
- H2O
O () ()
, .
4.4
) K 2 3
.
Br
KOH
) 41
3.
OH
H+
- H2O
4.6 A
p ,
. .
KEAAIO 4: A
134
4.6.1 K
K H2 (Pt, Pd, Ni Pd
Rh), ,
.
H H
C C
H2
C C
H2

Pd
T H2
. , , .
H2
H H
C C
H2

H ( ). ,
:
H
K ,

{
.
H R4
H
R4
H
R1
R1
R3
R2
R3
R2
, H2 1,2 cis1,2.
cis
CH3
CH3
H2
Pd
cis
CH3
H
H
CH3
CH3
CH3
135
H . A , trans cis (E 4.4). H cis trans , .. cis trans2, ,

(H) . K
(n). cis2 H=28,6 kcal/mol,
trans2 H=27,6 kcal/mol. E, trans2 cis2
28,627,6=1 kcal/mol.
H2
Ho = 28,6 kcal/mol
H2
To trans2
cis2 28,627,6 = 1 kcal/mol.
Hocis
Hotrans
Ho = 27,6 kcal/mol
28,6 kcal
27,6 kcal
CH3CH2CH2CH3
,
, , (
E 4.4).

H2C CH2
KEAAIO 4: A
136
4.2
H D2 H2,
, (cis)
(trans).
D2 (, ).
D2 .
H
C C
HOOC
COOH
COOH
C C
HOOC
E D2 o ,
D
, ;
4.6.2 . K Markovnikov
T
:
C C
HX
HBr
H X
C C
HX = HCl, HBr, HI
Br
HX
A ,
.. . ,

. ,
HBr 2 , 22
12.
22, 12 . ;
H3C
H3C
C CH2
137
H Br
H3C C C H
HBr
Br H
H3C C C H
H3C
H3C H
> 99%
< 1%
H
Markovnikov, : K (HX) , H
C , X, . ;
, HBr . A E 1.161.18,
, , , . H
. H+ *,
. , Br , . , , HBr.
C C
H
H
+
H C C
H
H
H Br
Br-
H Br
H C C H
H
H
T *;
K ,
. , , , . ,
CX
,
, , , , , X.
KEAAIO 4: A
138
R2
R1
C Br
R3
Br
R1
R2 C
R3

CX . O
sp2.
O sp2,
C 120.
K p .
p
R2
R1
R3
H
. T , . H
( E 2.9 4.4). :
CH3
H3C C
CH3
CH3
H3C C
H
H
H3C C
H
H
H C
H
M
HBr 2
,
. E
. Br
22,
Markovnikov.
139
:
,
T :
H3C
H3C
C CH2
H3C
H+
H3C
> 99%
C CH2H
H3C
CH
+
CH2
H3C
Br
Br-
Br
H3C C CH3
H
H3C C CH2Br
CH3
< 1%
CH3
4.5

.
HBr
HCl
4.6.3 H2O ()
T (.. H2SO4)
.
H2O
C C
H+
H OH
C C
OH
H2O
H+
H2O/H+
H H + ,
,
H2O () ,
. H , , , [H+] .
KEAAIO 4: A
140
H
H
H
H
H C C
H
H
H+
H OH2
H C C H
H
H
H2O
H OH
H C C H
H
H
H+
O
. A
Markovnikov, ,
. , 11
H2O/H+ 11,
, 22 , .
H
+ CH3
HO CH
3
H2O
H+
CH3
H+
CH3
HO
H2O
CH3
H+

4.6.4
T (Br2) (Cl2)
1,2.
C C
CH3CH = CH2
X2
Br2
X X
C C
CH3CHBrCH2Br
X = A
H , .. , . A ,
Br
, :
141
I {
Br
Br
Br
Br
Br
Br-
H
p
.
X
Br ,
CBr ,
. (A H2
4.6.1). ,
Br2 trans1,2 ( cistrans,
, E 2.10).
Br
Br2
trans
H
H
Br
4.6
Br 2
trans2.
Br2
H3C
CH3
4.6.5
E X2
H2O, 1,2,
1 2 X OH. A
Br2 H2O. A , H2O,
. H
Markovnikov, Br OH .
KEAAIO 4: A
142
Br OH
C C
Br2
C C
H2O
CH3
Br2
CH3
CH3
H2O
HO Br
CH3 C C H E Markovnikov
CH3
CH3
H Markovnikov ,
,
, .. 22. Br,
.
( 4.6.2). E, H2O , .
H3C

H2O
H3C
Br
+
OH Br
C C H
CH3
CH3
CH3
CH3
E Br2
, ROH,
, :
Br OR
C C
Br2
C C
ROH
Br
Br2
CH3OH
OCH3
CH3

Br2
(CH3OH).
4.7
:
Cl2
CH3CH = CH2
OH
Br2
H2O
143
4.6.6 E
A
. K ,
(BH3), (BR3). K,
H2O2
, B(OH)3.
, . A,
BH3 H2C=CH2 (CH3CH2BH2),

(CH3CH2)3B. T (CH3CH2)3B
H2O2/OH CH3CH2OH B(OH)3.
2
H
B H +
H
H
BH2
C
C
H
H H H
H
C C
H
H
C C
H3CH2C
H3CH2C
H2O2
OH-, H2O
3 CH3CH2OH
B(OH)3
E 4.6.3
, Markovnikov. ,
COH . ,
Markovnikov,
COH
.
Markovnikov 4.3.
O
. ,
22,
22 32,
:
B CH2CH3
KEAAIO 4: A
144
H+
HO
BH3
H2O
H2O2
OH
OH-, H2O
4.3
H BH3 , ..
, :
H
H
C
H
C
B
-
H H
H C C H
H BH2
H
H
H
Markovnikov 1.
4.6.7
T R2C:,
, , . T .
R{1{
C{
R{2{
K{
{
{
C,
, . K
.
R1
+
C C
C
R2
CH2
R1
R2
C
145
4.6.8
E
o Markovnikov. E
,
Markovnikov. O

(ROOR 2 RO) . :
H3C
H3C
H Br
H3C C C H
HBr
C CH2
ROOR
-Markovnikov
H3C H
A , Markovnikov
, HBr. O
, , ( 2.13.2). K , OO . , RO HBr (ROH) (Br).
H Br , ,
HBr,
Br . H
, .
RO OR
+
RO
Br
Br
C C
RO
HBr
C C
HBr
+ RO
ROH + Br
Br
C C
Br H
C C
+ Br
A , , , ..
22. H Br -
KEAAIO 4: A
146
: ( , 2.13.1). , Markovnikov .
T
()
H
Br
C C
H
CH3
CH3
Br CH
3
H C C
CH3
H
HBr

()
Br
C C CH3
H
CH3
H
- Br
HBr
- Br
H Br
H C C CH3
H CH3
Br H
H C C CH3
H CH3
K
4.8
;
Br
Br
4.6.9 A
T
1,2.
HO
C C
OH
C C
1,2-
H :
) E KMnO4 OsO4/NaHSO3,
cis.
) E (.. , CH3COOOH) H2O trans.
147
4.9
T cis2 KMnO4 trans2
CH3COOOH/H2O. E.
4.6.10. O
H (O3)
. T .
3O2
2O3
K .
,
. T Zn
CH3COOH, .
O
O
O
C C
O3
C C
O O
C
C
O
Zn
CH3COOH
C O
O3
O +
Zn/CH3COOH
E , ,
, , ,
cis trans, .
R1
R3
O3
R2
R4
Zn/CH3COOH
R2
R1
O3
R1
R2
R3
Zn/CH3COOH
R2
R1
O3
R2
R1
O +
R3
R1
H
O +
R3
H
O +
Zn/CH3COOH
R4
O
R2
C O
KEAAIO 4: A
148
, . ,
3,
1,4,
722,6.
7A22,6
O3
O
Zn/CH3COOH
+ O
4.10
K C8H12
. ;
O3
C8H12
Zn/CH3COOH
O
C
4.11
) T
:CH2
.
) H 2

.
) O
,
.
149
4.7 A
K (.. H+/H2O HBr), ,

. , HBr 3,31

Markovnikov, , 2
2,3,
3,31.
Br
H3C
H3C
CH3
Br
CH3
HBr
HBr
H3C
H3C
CH3
CH3
H3C
H3C
CH3
O . A . A
( Markovnikov),
. K , . , , Br 22,3.
H
+
CH2 .
H3C
EN
H3C
H3C
H3C
CH3
H+
CH3
H3C
CH3 M CH
3
H3C
H3C
CH3
H3C
CH3
T
Br
Br
Br
CH3
H3C
H3C
CH3
CH3
H3C
Br
H3C
CH3
CH3
KEAAIO 4: A
150
K
. O
. O H :
H
H3C
H3C
CH2
+
H3C
M H
H
H3C
CH2
+
CH2H
H3C
M H
CH2H
H3C

H . ; , . M

, HBr 3,31
.
4.12
A A B
:
HCl
Cl
A
Cl
B
YNOH
: O sp2
. O
120.
: E .
Cis, trans: X , . A .
E, Z: ,
. H CahnIngoldPrelog.
:
.
: H
.
K: M ,
. T sp2 .
H
. , . , (CH3)3C+ H3C+.
K Markovnikov: K HX (X= OH)
, X . H
.
I : E Br2 . Br .
Y: A , BH 3,
. T
H2O2 Markovnikov
.
Markovnikov: K Markovnikov
HX , X . H
.
151
KEAAIO 4: A
152
K: M
(:CR2). T . ,
.
: A
1,2. H
(KMnO4) (RCOOOH/H2O) .
O: A (O3)
C=C,
. ,
.
A : K H , . H

.
K 4
1. A, B, , , E, T Z, (
, ):
) A + H2/Pd 1,1
) B + HBr 2B
) + :CCl2 1,1
) + O3, Zn/CH3COOH CH3(C=O)CH2CH2CH2(C=O)CH3
) E + H3O+ 2
) T + Br2 1,24
) Z + BH3, H2O2/OH 1
2.
;
;
OH
;
OH
Br

, :

,
,
,
,
, ,

,
,
.

T CC
pKa
A
T
K Lindlar
O
KEAAIO 5: A
154

, CC (H3O+, HX, X2), (CCH). E,
25. H
,
4 5.
T 5 :
5.1
5.2 O
5.3
5.4 A
5.5 O
155
5.1
T
, CC. O (E 1.4.3)
sp (
), p ( ). O , sp .
sp, CC 180,
.
pp
spsp
pp
T CH22. O .
, CH3CH2CCCH3 2. T
, HCCH (), .
O (C=C)
(CC) .
, . E ,
. :
6
1E5
3
4
5 6
6M51
KEAAIO 5: A
156
A ,
. T CC
,
CCH. , CC (R1CCR2).
A
C C H
H3C C C CH3
5.1
T (C3C8), .. , . E.
K{{
K{{
5.2 O
T CCH . H
sp . s
,
CH. K , s ,
,
, p . E,
(sp)CH ,
CH, sp2 sp3. , CH . o CH, o
H , .
-
H+
Y sp
pKa . H CH CCH > C=CH > CCH.
Ka
H C C H
Ka
H2C CH2
H3C CH3
Ka
157
H C C
H2C CH
H3C CH2
H+
pKa = 25
H+
pKa = 45
H+
pKa = 60
K pKa
25 ( CH3Li), . O
, pKa CH4
NH3 pKa
( E 1.11.).
C C H
+ CH3Li
pKa ~ 25
H C C H
C C Li
+ NaNH2
CH4
pKa ~ 60
H C C Na + NH3
pKa ~ 25
pKa ~ 35
5.2

1; CH3COONa, KOH,
NaNH2, CH2=CHLi. pKa (CH3COOH: 5, H2O: 14, NH3:
35, CH2=CH2: 44).
5.3
( , pKa ~ 15).
2 CH3Li
HO
C C H
1 CH3Li
KEAAIO 5: A
158
5.3
O :
) A 1,2
H 1,2 .
( E 4.5) . T . K,
.
X X
C C
H H
X
+
+ KX + H2O
C C
KOH
1o
C C
C C
KOH
+ KX + H2O
CH2Br CH2Br
KOH
Br KOH
C C
H C C H
E 1,2 (. 4.6.4), 1,2 , :
H
C C
H
Br2
CHBrCH2Br
2 KOH
C C H
) A
T (. E 7.3) , ,
. M ,
,
.
159
R C C Na + R-X
R C C R
NaNH2
C C H
C C Na
+ NaX
CH3Br
C C CH3
5.4

:
H
Br
CH2Br
NaNH2
CH3CH2Br
H
C
H
5.4 A
O
.
.
5.4.1. A
T
H2 cis. M
.
R C C R
H2
H2
C C
cis
C C H
2 H2
Pd
CH2CH3
RCH2CH2R
KEAAIO 5: A
160
H ,
, Pd CaCO3, Lindlar. H (
4.6.1), cis.
R
H
R C C R
R
C
H
R
R
+
C C
H
H2

cis
H3CH2C C C CH3
H2
H
C C
H3CH2C
Lindlar
CH3
H ,
,
Na Li NH3. K ,
trans .
Na
R C C R
NH3
H3CH2C C C CH3
R
C C
H
Na
NH3
H
C C
H3CH2C
CH3
H
A, , , cis trans ,
.
5.4.2.
T (X2) (HX) ,
. K Br2, ,
Br
trans . A,
Br2 , .
161
Br
Br2
Br2
C C
R C C R
R
Br
2 Br2
C C H
Br Br
R C C R
Br Br
CBr2CHBr2
, , , ,
. H

Markovnikov, .
H
HX
R C C R
R
C C
R
C C H
HX
2 HBr
H X
R C C R
H X
CBr2CH3
5.1

,
. M ;
H
R
C C
HX
H X
R C C R
H X
5.4.3. E
T (H3O+)
HgSO4, . H Markovnikov, . A
(), ,
, .
KEAAIO 5: A
162
R C C R
H2O/H+
HgSO4
H O
R C C R
H
R
C C
OH
E
C C H
O
C
OH
C
CH2
H2O/H+
HgSO4
CH3
T , , . H
() .
T
H O
C C
E
()
H
C C
K
()
5.5

2.
5.4.4. O
T
Zn/CH3COOH .
( 4.6.10), , O3 .
, 3,
.
O3
R1 C C R2
Zn/CH3COOH
H3CH2C C C CH2CH3
R1COOH
O3
Zn/CH3COOH
+ R2COOH
2 CH3CH2COOH
163
5.6
() M
3,
2 H2O/H+ HgSO4.
H3C C C CH2CH3
O
H3CH2C C CH2CH3
() , Go<0.
OH
G < 0
() K
.
5.7
A :
A
()
()
O3
CH3CH2CH2CH3
H2/Pd/CaCO3
H3C
Cl
()
1 eq HCl
O
C
CH2CH3
CH3
H3C
H3C C C CH3
()
H2/Pd
()
H3O+/HgSO4
()
2 eq HCl
()
Na/NH3
H3C
CH3
CH3CH2CCl2CH3
CH3
H3C
CH3COOH
KEAAIO 5: A
164
5.5 O

25. ;
,
. A
,
. O . , , , 2.
2 , 1 2. E
HCl , 2.
CH3CH2CH3
CH3CH = CH2
Cl2
h
HCl
CH3CH2CH2Cl
CH3CH(Cl)CH3
CH3CH(Cl)CH3
H
. ,
. A
.
1
N meso3,4 ()
1 .
H
H3CH2C C C H
RX
HO
H
HO
CH2CH3
CH2CH3
meso--3,4-
165
:
E , . ,
. H meso3,4 ( 4.6.9)
cis3 KMnO4.
H
H
KMnO4
C C
H3CH2C
CH2CH3
HO
H
HO
CH2CH3
cis
CH2CH3
T cis3
3, Lindlar ( 5.4.1).
H2
H3CH2C C C CH2CH3
Lindlar
CH2CH3
H3CH2C
T 3
1 CH3CH2Br (E 5.4).
H3CH2C C C Na +
CH3CH2Br
H3CH2C C C CH2CH3
+ NaBr
, , meso3,4
1 :
H3CH2C C C H
NaNH2
CH3CH2Br
H3CH2C C C Na
H3CH2C C C CH2CH3
H
H2
Lindlar
H3CH2C
CH2CH3
KMnO4
HO
H
HO
CH2CH3
CH2CH3
2
N 4,
, .
H C C H
RX
O
H3CH2CH2C
C CH2CH2CH2CH3
KEAAIO 5: A
166
:
H C C H
NaNH2
NaNH2
H C C Na
H3CH2CH2C C C Na
H2O/H+
HgSO4
HO
H3CH2CH2C
CH3CH2CH2Br
CH3CH2CH2Br
CH2CH2CH3
H
H C C CH2CH2CH3
H3CH2CH2C C C CH2CH2CH3
O
H3CH2CH2C
C CH2CH2CH2CH3
5.8
X , ) CH3CH2CH2CHO, ) ) 52.
: O CC sp, . A .
O : T
sp
. K (.. NaNH2),
.
B: . H Markovnikov.
.
A : T cis
trans Na/NH3.
K Lindlar: A Pd CaCO3
cis.
Y N O H / E N I K A P O B H M ATA K E A A I O Y 5
167
E : M H2O/H+ ,

.
T: I , .
O : K , CC, .
K 5
1. ; ( )
H3CH2C C C H
H C C H
H3CH2C
CH3
( cis)
CH3CH2CH2CH2OH
2. 1,6 . N :
Cl
Cl
Cl
H C C H
.

, :
,
, ,
,
,
DielsAlder
.

1,2 1,4
A DielsAlder
scis

E
4
. C=C
, . H

. N -
KEAAIO 6:
170

, , )
, )
, ) DielsAlder .
T 6 :
6.1
6.2
6.3 A
6.4 K

6.5 A DielsAlder
171
6.1
(
) .
M
. , 1,3 , 1,4 . ,
A.
1,3-K{{
{
1,4-K{{
{
p-K{{
{

; H
( ),
.
H p . A , 1,3. A C2C3 , p
C2 C3. , C2C3 , . A
, .. C2 C4 1,4.
:
p C2
C3.
M :
p
C2 C4.
2
3
1
2
3
1
KEAAIO 6:
172
C2 C3, 1,3
C1C2 C3C4, C2 C3, (delocalization) . O .
, .
1,3,5,7,9-. T

.

,
,
,
.

C2 C3, 1,3,
CC. T C2C3
1,48 , CC
C=C. , H3CCH3 CC 1,54
, H2C=CH2 1,33 .
1,54
H3C
CH3
1,33
H2C
1,48
H
H
CH2
H2C
CH2
6.1
T .
; E.
2 H2
2 H2
Pd
Pd
173
6.2
O (E 4.5). ,
* * .
:
Cl
OH
KOH
H+
- H2O
- HCl
I
. ,
4
1,3, 1,4. Y .
H
KOH
Cl
H
KOH
. A
.
A.
.
6.2
;
Cl
Cl
2 KOH
OH
H+
HO
6.3 A
O
(E 4.6). ,
C X
* A .
C C
KEAAIO 6:
174
,
Markovnikov. , 2 HBr
1,4, ,
Br o .
E, Br 2 , ,
.
Br
Br
2 HBr
HBr
Br
1,4-
Br
Br
Br2
2 Br2
Br
Br
Br
Br
, . , Br2 1,3, : 3,41, 1,2, 1,42, 1,4. T

1,4
C2 C3. E, HBr
1,3 31 (
1,2), 42 ( 1,4).
1,4-
1,2-
CH2 = CH - CH = CH2
1
Br2
BrCH2 - CH(Br) - CH = CH2
BrCH2 -CH = CH - CH2Br
HCH2 - CH(Br) - CH = CH2
HCH2 -CH = CH - CH2Br
CH2 = CH - CH = CH2
HBr
T 1,2 HBr 1,3 Markovnikov, Br

.
, , 1,4; A
, .
A, H+ ,
. T
175
*,
(. . 173). (E 1.10),

. , Br 2 4,

{
1 2
H
3
H+
H
H
H
H 3C
H3C
H
Br-
BrBr H
H3C
H
H
H 3C
1,2- {
Br
H
H
1,4- {
A *
T
.
, .
, H+
1,3 ,
C1 C3.
H
H
H2C
H
H
H3C
H
H
H
H
H
2
Y
. T

C1 C3.
,
.
>
KEAAIO 6:
176
H
H3C
H
T

.
H
H
H3C
CH3
,
( 4.6.2):
CH3
H3C C
CH3
CH3
H C CH=CH2 > H C CH=CH2 H3C C

CH3
6.3
() T
A B :
+
CH2
+
CH2
A
() M HCl
1,3 ,
HCl
5,51,3

6.4 K

A HBr 1,3
( E 6.3). E +40 C, 1,2/1,4 = 15/85, 80
C 1,2/1,4 = 80/20. ;
, E 1.16. E
,
(G) . T .
A ,
. 80C,
(1,2) G (G1,2<G1,4). T 1,2 .
E , ,
. ,
. A
, ,
, , G. T
. , 1,4 (G1,4 < G1,2) .
Br
1,2
K .

Br
1,4
.
E
T ,
, Br
1,3. E G1,4 >
G1,2. , 1,2. E
( ), , , , 1,4 ,
1,2. , 1,2 -
177
KEAAIO 6:
178
1,2 1,4 , , 1,4 .
G1,4{
1,4
1,2
+ Br
Br
{
1,2
CH2CHCHbCH2 CH2CH -
--CH-
-- CH2 CH2CH2bCHCH2
G1,2{
1,2
Br
{
1,4
1,4
6.4
1,4 Br2 1,3 1,2; (Y: B E 4.4)
6.5 A DielsAlder
M
DielsAlder
. T
DielsAlder, . ,
1,3 ()
. O
( ) ( ). O
,
. A (E 1.15).
A D I E L S A L D E R
179
M Diels-Alder:
O
.
+
1,3-
T DielsAlder :
) H ,
, .. CN, C=O, NO 2,
COOH, . , , :
O
H
CN
NO2
) DielsAlder,
scis .
. H
strans . T 1,3, ,
,
(scis)
DielsAlder. H
scis strans, (
trans cis , E 4.4).
H
scis
H
H
strans
scis DielsAlder. ,
2,52,4
, scis
strans,
.
KEAAIO 6:
180
CH3
CH3
H3C
Keq >> 1
scis
H3C
CH3
CH3
strans
CH3
CH3
T , , , scis.
strans. T
Diels-Alder.
O DielsAlder .
E , ,
1,3, ,
DielsAlder
1,3 .
O
O
+
CN
+
CN
A D I E L S A L D E R
181
6.5
A ,
.
CN
;
O
O
O
O
6.6
1,3
.
;
F
F
C C
H
C C
KEAAIO 6:
182
:
. T .
: .
/ :
1,2 1,4. T 1,4
. O
1,2/1,4 .
A : K . E ,
, .
.
K : Y
G
. Y
, G
. O
,
.
A DielsAlder: A
() .
scis. K
.
,
, .

, :
(CX),
CX ,
,
, ,
,
,
, Saytzef,

SN1 SN2,
, ,
SN1 SN2,

E2 E1.

H
K Saytzef
HX
A Walden
M SN1
KEAAIO 7: A
184
M SN2
HX
E
H .
M

,
. , , , , , .
T 7 :
7.1
7.2
7.3 A
7.4 A . M SN2
7.5 A . M SN1
7.6 A . M E2
7.7 A . M E1
185
7.1
T CX, X = F, Cl,
Br I. O sp3 p . A ( I> Br > Cl > F) p
, sp3(C)p(X) . , I 5p,
F 2p. , sp3(C)5p(I) sp3(C)2p(F). ,
: CF > CCl > CBr > CI.
X CX
.
T (), (+). E , , . H C+X
, .
+
X =
H o (E 2.3). H , . E,
, .
, 36 63 36.
1
5
2
Cl
O
8
8
2
1
Cl
KEAAIO 7: A
186
7.1
O :
F
I
A
Cl
7.2
T :
) A . H
E 2.122.14. K
. M
( E 2.14). A, . H
,
. ,
. A, , .. , .
R H + X2
CH3
H3C C CH3
CH3
CH3
H3C C CH3
H
Cl2
h
Cl2
h
R X
+ HX
CH3
H3C C CH2Cl
CH3
CH3
H3C C CH2Cl
H
,
.
CH3
H3C C CH3
Cl
) (HX) . H 4.6.2 4.6.8. X

(-
187
Markovnikov) ( Markovnikov).
HX
C C
Br
H X
C C
HBr
HBr
ROOR
Br
) E (HX) . O .
R OH + HX
CH3CH2CH2CH2OH
R X + H2O
HBr
H2O
CH3CH2CH2CH2Br
) A SOCl2. H . O
.
R OH
SOCl2
R Cl + HCl
+ SO2
7.2
1 1.
7.3 A
) Y
M

(Nu)
,
. T :
R X + Nu
R Nu
KEAAIO 7: A
188
, ..
OH, CN ., , Lewis, .. H2O, NH3 . H
X , Nu, . 7.1
. , CN, (RCN),
NH3, ,
( 5.3.2), .
7.1

RX + OH ROH + X
RX + H2O ROH + HX
RX + RO ROR + X
RX + CN RCN + X
RX + NH3 RNH2 + HX
RX + SH RSH + X
RX + RCC RCCR + X
RX + RLi+ RR + LiX
O
(SN2)
(SN1). , (7.4 7.5).
) A ()
H
. E 4.5 . K
, , CX C=C. T :
H
R C
H
OH
H
C H
X
189
H
C C
+ H2O + X
O (E2) (E1).
O E 7.6 7.7.

( Saytzef). ,
CH3ONa 11
.
Br
CH3
CH3O-Na+
CH3
K
(T )
CH2

( )
H . E 4.4
, . ,
.
7.3
:
CH2Br + KCN
()
() CH3CH2CH2I + H C C Na
() CH3CH2CH2I + NaNH2
() CH3CH2CH2I + CH3ONa
7.4
:
KOH
KOH
Br
Br
KEAAIO 7: A
190
7.4 A . M SN2
O
,
. H
, . , , ,
RX
X , .
7.4.1 M
M SN2
:
) H , RX, , Nu ( , ' SN2).
T = k [RX] [Nu]
) A . H ,
X .
SN2
S OH,
R, .
A
B
C
Nu
H 3C
H
C Br +
OH
M SN2.

CH3
HO C H
H3CH2C
Br
CH2CH3
(S)
(R)
M , SN2
: T (Nu) (X).
A . M S N2
191
K CNu CX, ,
Walden. O CNu CX .
. ,
, Nu, , X. T
Nu X ( 1/2
, 1).
Nu
C X
Nu
Nu C
+ X
M SN2 .
O
, Nu C X.
7.4.2. X SN2. O
H SN2 ,
. ,
. ,
SN2
OH :
R Br + OH
H
H C Br
H
H
H3C C Br
H
R OH + Br
H
H3C C Br
CH3
CH3
H3C C Br
CH3
SN2
OH-.
KEAAIO 7: A
192
K , ,
,
. ,
CH3Br C
, , (CH3)3CBr, , , .
Nu:
Nu:
H
H C Br
H
H3C
H3C C Br
H3C
Nu
H H
C
H
H3C CH3
Nu
C
X
CH3
7.4.3 X S N2. T
; (
). A ,
,
. O .
, ( E
1.11 ,
). ,
OH > CH3COO > H2O. K H2O (pKa = 14) < CH3COOH (pKa = 4,7) < H3O+ (pKa =
1,7). , I > Br > Cl > F,
, HI > HBr > HCl > HF. A
A . M S N2
. , ,
( ),
. ,
, CN > I > OH > H2O.
R Br + Nu-
R Nu
Nu- = CN-
I-
HO-
+ Br-
H2O
7.4.4 X SN2. H
SN2 . E,
CX, X
,
X, . E X
, ' X, X. ,
I > Br > Cl > F > OH,
I ,
OH.
R X + Nu
X = I
Br
R Nu
Cl
OH

Nu RX
7.4.5 X SN2. O
H SN2. ,
, .
193
KEAAIO 7: A
194

H ().
O , .. , ,
, .. (CH3)2S=O H2O,
. O ,
OH NH , .. H2O CH3OH,
, .. CHCl3, (CH3)2SO, CH3CN
. H , ,
, , .
.
O
OH+ NH+,
, O N.
RO H
OR
H+
R
O
O +
X- H OR
H +
OR
O
R
O
R
E

, .. .
E

, .. .
O
, .. O N, .
CH3CN
CH3CN
CH3CN
NCCH3
E

CH3CN.
A . M S N2
195
O , .. H2O, SN2, , . A, , , .. CH3CN (CH3)2S=O,

, ,
, . . NaCN,
, Na+, CN.
7.5
) K CN, A
B SN2.
A
Br
CH3
CH2Br
) H A
B (o

SN2).
A
NaCN
CN
CH3COONa
+ NaI
OCOCH3 + NaI
) H

SN2 :
H
H
H3C
H3CH2C
C Br
NaCN
H3C
H3CH2C
C CN
>
KEAAIO 7: A
196
) H A
B (o

SN2).
NaCN
CN
NaCN
Cl
CN
) H CH3CN

SN2:
NaCN
) H SN2,
, :
+ NaCl
OCH3
+ NaI
CH3O-Na+
I
+ NaI
CN
+ NaI
7.5 A . M SN1
7.5.1 M
SN2, SN1 :
) E
( ), .
A
Nu
C X
SN1
Nu-
50%
+ B C Nu
M SN1:

.
50%
) H RX
.
T = k [RX]
A . M S N1
197
, SN1
: T (RX)
(CX) (R+) X. ,
(Nu) (RNu). T RX . , RX , SN2. E ( 4.6.2),
. E, , 5050%
R S, .
+
C X
X-
Nu+
Nu C
M SN1: C-X

, {
{
{
,
o .
C Nu
7.5.2 X S N1. O
SN2, SN1
. :
H
H C Br
H
H
H3C C Br
H
H
H3C C Br
CH3
CH3
H3C C Br
CH3
SN1
.
K , , (. 4.6.2). , H2O SN1, tert-
KEAAIO 7: A
198
2, .
CH3
H3C C Br
CH3
CH3
H3C C
CH3
Br
CH3
H3C C Br
H
CH3
H3C C
H
Br
T tert

2,

.
7.5.3 X SN1. T
E , , ,
SN2. , SN1 , tert (CH3)3CCN
(CH3)3COH CN OH ,
, (CH3)3C+.
CH3
H3C C Br
CH3
CH3
H3C C Br
CH3
CN
H2O
OH
H2O
CH3
H3C C CN
CH3
CH3
H3C C OH
CH3
M SN1:
O

.
7.5.4 X SN1. H
O SN1 SN2
( 7.4.4). , CX
. ,
SN1, (CH3)3CI , (CH3)3CCl,
.
A . M S N1
199
7.5.5 X SN1. O
O ( )
SN1 . K , , . H . ,
H2O ( ), CH3CN ( ) , O N , .
. T
H2O , .
H
H
:
O:
:O
:
:O
O:
H
H
H
H
H
H
7.6
) SN1,
CN, A
B.
A
Br
CH3
CH2Br
H
H3C
H3CH2C
C Br
I
Br
) K
A B
I,
. SN1.
A
I C
CH3
CH2CH3
B
>
KEAAIO 7: A
200
) H tert

CH3COO
SN1 ,
OH.
) H 2
OH

2.
, SN1.
) M
(CH3CN) ,

(CH3CH2OCH2CH3). , SN1.
7.6 A . M E2
7.6.1 M
H
E2 , (RX),
.
T = k [RX] [B]
H E2 ,
H , X,
:
B{
H{
R{ C
H{
H{
C H{{
X{
B{
H{
R{ C
H{
H{
C H{{
H{
H{
C C { +{H{2{O{ +{ X{{
R{
H{
X{
M E2:
O {B{{H{, C{=C
{ , {{
C{H{ C{{X{ .{
A . M E 2
201
7.6.2. X E2
) A E2 :
(E 2.5).
B

E2,
H X
.
, HBr
(1R,2R)1,21,2 , (Z), , HBr (1R,2S)1,21,2, (E). K ,
E2
Br .
H
Br
H
CH3
Br
Br
CH3
CH3
B
H3C
H
Br
HBr
(Z)
H3C
CH3
CH3
(E)
HBr
H
Br
(1R,2R)
Br
CH3
(1R,2S)
E, HCl trans1
2, 31 11
. O 11 H Cl trans, , trans Cl CH3.
B
H3C

Cl
trans H
.
H
H
Cl
H
CH3 H
H3C
A ,
Cl H
cis.
KEAAIO 7: A
202
) H E2 , X. , , Br Cl F.
H H
R C C Br
H H
H H
R C C F
H H
H
C C
HBr
H
H
C C
HF
) H E2
. ,

NaNH2, NaOH, NH 2
OH.
H
H
C C
NaOH
HBr
H H
NaNH2
R C C Br
HBr
H H
H
T
C C
R
) M E2
, ,
.
, (E2) (SN2). O .
:
H
H
C C
H H
R C C X
HX
H H
Nu
Nu
X
H H
R C C Nu
H H
E E2 ,
(E2 SN2), , . , / , . M ,
A . M E 2
203
,
,
( ) .
7.7
) K OH, 2
/
1 (Y:
E2 SN2).
) E2,
cis2 D.
D
H
H
Br
CH3
CH3
) ,

(SN2 E2),
I,
.
H
H
C C
H H
I
R C C X
HX
H H
I
X
H H
R C C I
H H
K
)
14,
,
41.
1 eq B
Br
HF
Br
KEAAIO 7: A
204
7.7 A . M E1
T
E1
RX . Y
E1 SN1.
T = k [RX]
O . ,
CX
(R+) X. T
H+ . O
E1 , .
CH3
H3C C Cl
CH3
CH3
H3C C
CH3
Cl
M E1
CH3
H3C C
H C H
H
H3C
H
C C
H3C
, E1 SN1 . E ,
. , tert ( ) ( ).
CH3
H3C C Cl
CH3
OH
H2O
CH3
H3C C OH
CH3

H3C
H3C
H
C C
H
YNOH
205
7.8
(A B),
E1;
CH3
Br
Br
7.9
K HCl trans12
E2, 31
11 ( 7.6.1). K, , E1, 11.
;
B
H3C
H
H
Cl
E2
H
CH3 H
E1
H3C
A: O . H CX : CF > CCl > CBr > CI.

, C+X.
.
: ) M ,
) HX , )
) SOCl2 ( ).
: A
(X) (Nu),
X (RX +
Nu RNu + X). A , ..
, , , .
KEAAIO 7: A
206
A : K ,

.
K Saytzef: K HX ,
,
.
M SN2:
,
, NuCX. E
X ( Walden).
X SN2:
) H SN2
. , .
) H SN2 . H .
, .
, OH CH3COO,
pKa H2O pKa CH3COOH. E , I > Br >
Cl > F, .
) H SN2
X. H .
, . , I
F, pKa HI
pKa HF.
) H SN2 , , .. CH3CN , , .. CH3OH. T
.
YNOH
M SN1:
CX,
. E ,
.
X SN1:
) H SN1
. ,
.
) H SN1
, .
) RX, , .. , SN1
X, SN2.
) H SN1 , , . T

.
M E2: . H E2 X . O SN2 E2 ,
.
M E1: K , , H+
. E
SN1,
.
207
KEAAIO 7: A
208
M
SN1
M
SN2
M
E1
M
E2
RCH2X
R2CHX

E2.

SN1.
T
R3CX
K 7
1. T SN2:
) CH3CH2CH2Cl
) CH3CH2CH2Br
) CH3CH2CH2CN
2. T SN1:
()
()
()
3. . E
:
H D
Br
H D
Br
D H
CN
H D
CN
,

.

, :
,
, ,
, Hckel,
,
, , , ,
FriedelCrafts ,

, ,
, ,
,

.

, ,
A FriedelCrafts
K Hckel 4+2
A Clemmensen
K E A A I O 8 : B
210
A WolffKishner
E
T
. B

. E 1.10,
. O ,
, ,
, , .
T 8 :
8.1 O
8.2
8.3 K . O Hckel
8.4 A . O
8.5 N, , , Friedel
Crafts
8.6 E

8.7 E
8.8 H
8.9
8.10 A
211
8.1 O
A
. O , , ,
, ..
, :
H3C
S
N
H
B
O
O
H
HO
H Ph . , () :
CH3
Ph-CH3
-CH3
O , . (E 2.6), , ,
. ,
. :
5
Cl
CH2CH3
2
3
T , , , 2, 3 4, ,
. , ,
.
:
K E A A I O 8 : B
212
CH3
Br
Cl
H3C
, IUPAC. . , IUPAC . , ,
.
CH3
T
()
COOH
NH2
OH
A
(A)
()
OH
H3C
Br
8.1
O IUPAC. .
CH3
) H3CH2C
Br
)
2
NH2
8.2
T . E , ,
, .. Br2 , ,
. , , E 8.5.
213
Br
Br2
Br
Br2
Br
Br
; E
1.10
,
,
. A , .
T , 120,

.
H
C
C
C
C
H
8.2
K
28,6 kcal/mol. H
H2, , 49,8 kcal/mol.
; (Y: E ,
3 28,6 = 85,8 kcal/mol.)
3 H2
H2
K
H = 28,6 kcal/mol
H = 49,8 kcal/mol
K E A A I O 8 : B
214
8.3 K . O Hckel
A , ,
. Hckel,
p
, 4+2 , = (0,
1, 2 .). T , , , Hckel = 1. E,
, , ,
.
A
Hckel
6
10
14
E ,
4+2 . O
. A,
. , 1,3
1,3,5,7, , , , , Hckel. ,
.
1,3K{
A 4
{
1,3,5,7K
A 8
{

, {

{.
K . O H C K E L
215
M CC
C=C, 1,3 , .
T 1,3

.
8.1
T ,
(, , E
6.3, ).
, .
H
H
H3C
H
H
H3C
H
H
H3C
H
H
H
H
H
H2C
H
H3C
H3C
H
H
E,
, ,
.
.
K E A A I O 8 : B
216
8.3
8.2,
1,3,5,7 .
4 H2
H = ;
8.4 A .
O
E ,
. , , .

. T :
H
H
H
H
+ E+
H
+ H+
H
H
E =
H (E+)
.
. A
:
H
H
E+
H
H
H
H
E
+ BH+
H
H
A . O
217
T , , E+,
. A 4.6.2 4.6.3, E+
H+
. T ,
, , (6 ).
H
H
E
+
+
H
+
H
H
H
H
Y
K, H+ ,
H E. H ,

.
8.4
M ,
, .
G.
K E A A I O 8 : B
218
8.5 N, , , FriedelCrafts B
,
(E+) .
8.5.1 N
H
.
NO2
HNO3
H2SO4
T
(NO2+),
: T
HNO3 H2SO4, (H2NO3+) HSO4. T H2NO3+
H2O, , .
O
O N
O
H2SO4
+ O
O N
+
O
H
HSO4
H2O
2+
N O
+NO
2
T ,
. H H
H2O ( ).
H
H
NO2
H
+NO
2
H
H
:OH2
H3O+
NO2
H
H
8.5.2
H ( ) ,
H SO3H, , H2SO4 SO3. T
N, , , FRIEDELCRAFTS B
219
(HSO3+), , .
O
S
O
+
H O
H2SO4
S
O
HSO4
H O + O
S
O
T HSO3+
HSO4 () .
H
H
H
H O+ O
S
O
H
SO3H
H
HSO4
+
H
H
H
H2SO4
SO3H
8.5.3 A
H (X2) ,
Lewis , Fe(III). A , , Br2/FeBr3. T FeBr3,
Lewis, Br2. ,
BrBr Br+ FeBr4,
Br+.
Br
Br
Br
FeBr3
Br FeBr3
+Br .... FeBr

4
O Lewis
T Br+ , H FeBr4 .
H
H
H
H
Br+
H
H
H
Br
H
+
H
H
Br
FeBr4
+ FeBr3
H
H
H
+ HBr
K E A A I O 8 : B
220
8.5.4 A FriedelCrafts
H FriedelCrafts ,
,
. T (R+). T
Lewis, .. AlCl3.
R
RCl
A Friedel-Crafts
AlCl3
T , .. RCl, Lewis
, CCl. ,
R+ AlCl4,
R+, .
R Cl
+R...AlCl
4
R Cl AlCl3
AlCl3
O Lewis
T R+
AlCl4 .
H
H
R+
H
H
H
H
+
H
H
H
AlCl4-
+ AlCl3
H
+ HCl
H
H
E E 4.7 ,
.
, FriedelCrafts,
. , CH3CH2CH2Cl/AlCl3 , , n.
N, , , FRIEDELCRAFTS B
CH3CH2CH2Cl
CH2CH2CH3
AlCl3
CH3
C CH3
H
O ,
H n
, :
H
H
H
C+ H
C
C
H
H
H
H
H
C
H
C
C+
H
H
H

()

()
8.5.5 A FriedelCrafts
H FriedelCrafts
FriedelCrafts
(RCOCl) AlCl3. K FriedelCrafts .
RCOCl
AlCl3
O
C
A Friedel-Crafts
T RCO+ AlCl4,
RCO+. T R+ FriedelCrafts. T RCO+
, .
O
R C Cl
+
R C O
O
R C Cl AlCl3
AlCl3
R C O+
RCO+...AlCl4
A :
O

( 8.5.4).
221
K E A A I O 8 : B
222
8.2
A ,
. ,
. E :
CH3
C CH3
CH3
H+
H+
H2C C
CH3
CH3
8.5
:
CH3
+ H3C C CH2Cl
CH3
AlCl3
CH3
C CH2CH3
CH3
8.6 E
) T
O
, : ) )

. O , . , : PhCH3 > PhH > PhCl. K ,
CH3 (+I ) ,
().
. A, Cl
I, () .

. H
CH3 +I {
, -Cl {
-I
.
Cl
CH3
>
>

. A
(PhCHO). H C=O

. ,

. E,
CHO ,
, .
O
H
C
H
C
A , , PhOH. H OH,
I , ,
( ).
O H
O H
O H
)
O . Y -
O H
223
K E A A I O 8 : B
224
, . 8.1
, . , .
8.1
Y
Y
Y
E
E+
+
E
A, OH, NH2, NHCOCH3
NO2, CN, COOH, CHO,

COR
F, Cl, Br, I
8.6
, NH2 CN , . Y , , PhNH2, , PhCN.
NH2
C N
225
8.7 E
8.7.1 E
8.1 , (OH), (NH2), . O

(), (OH NH2).
A ,
, .. . (PhCH3)

, . E
( ). T
,
. E, .
CH3
CH3
+
H
E
+
CH3
H
E
H
E
2o
CH3
CH3
E+
2o
CH3
CH3
+
H
E
2o
CH3
H
E
H
o
E 2
CH3
CH3
+
+
o
H 2
3o
+
E
2o
K E A A I O 8 : B
226
A ,
OH. A ,
,
, OH
, :
+C
+
O H
O H
A OH
I
,
, , .
+
OH
OH
OH
OH
H
E
H
E
H
E
+
H
E
+
OH
OH
+
E+
OH
OH
+
H
E
H
E
+
+
OH
OH
OH
H
E
OH
+
E
+
E
, ,
PhNH2, ,
NH2 ,
.
227
8.7.2 A
. E I
. ,
, , , . ()
; A ,
,
.
T I . E,
, ( 5.1 5 K).
+C
+
Cl
Cl
M ,

(PhOH) .
+
Cl
Cl
Cl
Cl
H
E
H
E
H
E
+
H
E
+
Cl
Cl
E+
Cl
Cl
+
H
E
H
E
+
+
Cl
Cl
Cl
H
E
Cl
+
E
+
E
K E A A I O 8 : B
228
T ,
I
, ,
.
8.7.3 A
, I , . A , ,
(PhCHO).
,

, . A, ,
,
(CHO). E,
.
O
C
H
E
H
C
H
E
+
H
E
+
E+
+
H
E
H
E
O
+
E
H
C
+
E
H
E
229
8.7
.
Cl
H3C
NO2
NO2
H3C
OH
8.8
H A
, B . A ,
.
CN
B
8.8 H

,
. , .
O , . M
,

.
K E A A I O 8 : B
230
8.8.1 H
K

1 2. 1 2.
E
8
E+
6
4
E ,
1. A ,
,
.
E
H
+
E
+
+
1
+
+
E+
+
2
E
H
E
H
H E+ 1 2 ,
231
. A
2, . A, 1 . , 1
2. E, 1
, 2.
8.8.2 H
K , 1, 2 9. E
9.
E
E
8
1
2
7
6
E+
3
5
10
A
.

9,
.
H E
H E
+
M 1 2

.
K E A A I O 8 : B
232
8.3
H
N C. H
3. M ;
4
3
2
N1
E+
8.9
T
FriedelCrafts . , . E

, , , .
R
RCl
RCl
AlCl3
AlCl3
RCl
AlCl3
, ,
FriedelCrafts , C=O CH2. K , COR
(), .
RCOCl
AlCl3
O
C
H
C R
H
H C=O CH2 : )
Clemmensen, ) WolffKishner ) .
233
H Clemmensen
ZnHg HCl. :
O
C
Zn-Hg
CH3
CH2CH3
A Clemmensen
HCl
H WolffKishner (H2NNH2) . :
O
NH2NH2
A Wolff-Kishner
NaOH
T, , . H . :
O
C
CH2CH3
H2
Pd
CH2CH2CH3
8.9
;
CH2CH2CH2COCl
8.10 A

: ) )
.
K E A A I O 8 : B
234
8.10.1 O
A , KMnO4,
, ,
, .
:
KMnO4
CH3
COOH
KMnO4
COOH
CH2CH2CH3
KMnO4
H3C
CH3
HOOC
COOH
H
CH . , C(CH3)3, .
CH3
CH3
H3C C
CH3
COOH
KMnO4
CH3
H3C C
CH3
, ..
, NO2 . .
:
Br
CH2CH3
KMnO4
Br
COOH
8.10.2 A
H (X2) ( E
2.122.14) N
(NBS) N (NCS) , , . K
.
Cl2
CH3
235
CH2Cl
O
ROOR
CH3
N Cl
CH2Cl
N H
O
O
N
K ,

( ). H
. ,
11. A, 11 90%,
12 (10%).
CH2CH3
Br2
h
Br
C CH3 +
H
> 99%
CH2CH3
Cl2
h
Cl
C CH3 +
H
90%
CH2CH2Br
< 1%
CH2CH2Cl
10%
,
E 2.14.
M , , .
, , ,
,
; A
( ).

, .
K E A A I O 8 : B
236
8.10
X
, A B:
H3C
H3C
A
CH3
COOH
A : Hckel,
4+2 . E Hckel .
, , : O 2, 3 4 .
H : K , ,
. O . T
.
N :
(NO2+),
HNO3 H2SO4.
: (HSO3+), H2SO4 SO3.
YNOH
A :
(X+), (X2)
Lewis, .. FeX3.
A FriedelCrafts :
(R+) (RCO+),
(RX) (RCOX)
Lewis, .. AlCl3.
H : ,
, .
: E ,
. O
.
A: FriedelCrafts
CH2, Clemmensen
(ZnHg/HCl) WolffKishner (NH2NH2/OH)
. A FriedelCrafts
.
A : ) M ,
. ) H , .
237
K E A A I O 8 : B
238
K 8
1. FriedelCrafts
, . E.
H
Br
H3C
CH2CH3
AlCl3
H
*
H3C C CH2CH3
P
(S)
2. :
D
3. () () ;
4. E :
CH3
Cl
Ph
AlCl3
CH3
A A A
1.1
) Be (1s2, 2s2),
) B (1s2, 2s2, 2s1),
) Li (1s2, 2s1),
) Cl (1s2, 2s2, 2p6, 3s2, 3p5).
1.2
) ,
, ( )
( ),
Lewis ,
. Kekul
C H. ( N O).
H
H
H C
C
N
C
H
N
Lewis
C
O
H C
H
H
O
H
C
C
C
C
H
C
C
H
1.3
H
Cl
T 1s, H
Cl
T 3p, Cl
T 3p, Cl
Kekul
H
H
H
H
Cl
T 3p, Cl
Cl
M H-Cl
Cl
Cl
M Cl-Cl
O , M O A
240
1.4
T , CBeC,
sp Be, 180,
120.
E , ! T .
1.5
: B, E.
E: , .
T: A, T, Z.
) T N sp3, (CH3)3N . CH3
.
:
N
H3C
CH3
CH3
) T Be sp , 1s
. E, .
) O sp2. E,
.
) (), C sp2,
.
) HCCF sp
o F H, .
) CF4 sp3
F. , .
) HOF sp3,
.
:
O
F
H
A A A
241
E , !
.
A , , .
1.6
) H3CLi+,
) H3CMg+CH3, ) H3C+OH, ) H3C+NH2.
1.7
1.3,
CH3H (D=104 kcal/mol) HCl (D=103 kcal/mol), CH3Br
(D=70 kcal/mol) II (D=36 kcal/mol).
1.8
H : B > > A. H B
CbO CCl, CbO.
A, =0.
1.9
) . sp Be, BeF2
BeF. E, =0.
) . sp2 , B+Br 120,
.
Br
B Br
=0
Br
1.10
() ( ), ( ). () (H),
.
O , M O A
242
O-
C
-O
O-
O-
1.11
) . H BeH2 Lewis Be
.
H Be H
) . E pKa HCN > pKa HF, F
CN.
) . T CH3OCH3
( Lewis)
H+ ( Lewis), .
H
O
CH3
CH3
H+
+O
CH3
CH3
1.12
() = , () = A, () = M, () = Y.
1.13
M 1.3, B 2 kcal/mol
A. , A
CH (98 kcal/mol) + ClCl (58 kcal/mol) = 156 kcal/mol. O
CCl (82 kcal/mol) + HCl (103
kcal/mol) = 185 kcal/mol. A 29
kcal/mol. B
31 kcal/mol. E , B.
1.14
T (), (G= 10 kcal/mol). M (),
G (G = 10 kcal/mol).
A A A
243
1.15
) E.
) H .
) A, B.
1.16
) . H
, ,

.
) . . M G .
) . E
, . M , . K
, , /
. T
. E , E 1.16. A
.
2.1
M .
2.2
Yo C.
1
2
2
2
1
3
1
2
3
1
1
1
4
3
2
1
1
1
O , M O A
244
2.3
3A6
2,3,6,7T
3A4
2.4
4,4,5T
OXI
5,5,6T
4A3,3
OXI
4,43
2.5
) . O E 2.5, .
) . H gauche ClCH2CH2Cl , CCl .
,
CCl .
1
H
Cl Cl
Cl
Cl
H
H
H
H
2 > 1
H
gauche
) . H .
) . T 2,2
, ,

CC, .
H
CH3
H CH3
H3C
CH3
H
H3C
H
CH3
A A A
245
2.6
A: 1K3
B: 1M2
: 1B4.
2.7
1,2 . , CH3CH3
. , CH
.
H3C
H
CH3
H
H
H
H
E
2.8
) . O ,
.
) . 2.3 CN
0,2 kcal/mol, Br, 0,5
kcal/mol. E, / .
) . O ,
,
.
) . H
, (G < 0).
O , M O A
246
2.9
H2
CH3
CH3
Pd
CH3CH2CH2Br
Na
Br
CH2CH2CH3 +
n-
n-
Br
CH3CH2Br
- LiBr
2 Li
CH2CH3
CH3CH2Li
2.10
+
Cl
D2O
Mg
MgCl
- Mg(OD)Cl
D
H
D
H
2.11
H2
Pd
Br
Br
Na
CH3Br + 2 Li
- LiBr
CH3Li
2.12
H .
CH3-H +
F-F
CH3-F
H-F
I kcal/mol: C-H (104) + F-F (38) = 142

H = - 102 kcal/mol
I kcal/mol: C-F (108) + H-F (136) = 244
A A A
CH3-H +
Br-Br
CH3-Br
247
H-Br
I kcal/mol: C-H (104) + Br-Br (46) = 150

H = - 8 kcal/mol
I kcal/mol: C-Br (70) + H-Br (88) = 158
2.13
H
:
CH3
>
CH3
>
CH2
2.14
K
. E (), !
,
. E () (),
. M
E 2.13 2.14.
2.15
) . M ,

. M
H .
) . T , ..
(
2),
.
Cl2
h
Cl
O , M O A
248
) . Y ( 1
tertBu, 1 , 2 3). E, .
Cl
Cl2
Cl
+ Cl
Cl
3.1
*
H
N
*
* OH
H
H3CO
H
H H
N
S
*
O
O
* *
CH3
CH3
COOH
3.2
A. T
B. T
. E
. T
3.3
(R) (R)
(S)
Cl
HO
H
(R) O (S)
CH3
H
H
H H
N
S
O
O
N
O
CH3
CH3
COOH
(S)
3.4
x % R y S . M x(+80) + y(80) =
40, x+y=1, x = 25% (R) y=75% (S).
3.5
A.
B. E
B, C.
A A A
249
3.6
H , , ,
.
Br
Br
3.7
) . E R, []D
. [45/100 x (+35) + 55/100 x (35)] = 3,5.
) . T cis1,2, , ,
. , .
H3C
CH3
) . O , []D.
[]D .
3.8
D (S)
OH
Cl
(R) CH3
(R)
CH3
H
CH2Cl
OH
H
H
3.9
) . K .
Br2
CH3CH2CH3
Br
) . T , {(S)2 (R)2} .
Cl
Cl2
h
*
(50% R + 50% S)
Cl
+
Cl
O , M O A
250
) . T 22 ,
Cl2 .
()
CH3
Cl2
()
Cl
()
CH2CH3
(S)
50%
CH2CH3
()
H3C
H3C
H3CH2C
F (R)
C Cl 50%
) .
, R S.
(R)
C
CH2CH3
H3C
H (S)
Cl2
h
ClH2C
CH2CH3
) . T 2 R
S , []D = 0, 1 . E,
,
.
4.1
) 1M1
) 1,4E
) 1A21
4.2
CD3
Cl
CH3
E,E
4.3
) . T E Z , .
A A A
251
) . cis2,2,5,53
cis tBu ,
cis2 . E, cis trans 2,2,5,53 0.95 kcal/mol cis
trans2.
H
cis
H3C
H
H3C
H3C
CH3
trans
CH3
H3C
CH3
H
H
CH3
H3C
CH3
CH3
H3C
H3C CH3
CH3
H
CH3
) . M
C=CC 120
12060=60,
10960=49 ( E 2.7).
4.4
) . 1, cis2 trans
2.
Br
KOH
+
) . K 3 : 41 31. E,
41.
OH
H+
H2O
4.5
HCl 1
Markovnikov. , 322
O , M O A
252
,
.
Cl
HCl
Cl
CH3
CH3
H Br
HBr
Br H
+
4.6
K Br2 trans2 R,S.
Br
Br
H
Br2
CH3
H3C
H3C
H
CH3
H
Br
Br
(R,S)
CH3
CH3
4.7
Cl2
Cl
O
CH3CH = CH2
OH
Br2
H2O
OH
Br
4.8
Br
HBr
HBr
Br
RO
4.9
K cis2 KMnO4
R,S. K
trans2 CH3COOOH/H2O R,S.
A A A
253
OH
H
CH3
KMnO4
HO
CH3
(R,S)
CH3
CH3
OH
H
CH3 CH3COOOH
H3C
H3C
OH
CH3
H2O
4.10
O3
O
C
Zn/CH3COOH
4.11
) . O ,
1,5 ,
1,4 .
O3
2
Zn/CH3COOH
O
O3
Zn/CH3COOH
O
+
) . K
.
CH2
X
CH3
(R,S)
OH
HO
CH2
) . H 2 2, , 3. K
CH3
O , M O A
254
1 1. H
2
H2O/H+ 1.
OH
BH3
H2O2/OH-
OH
4.12
M H+ ,
A. O B
, ,
, Cl B.
H+
M H
Cl-
ClCl
A
Cl
B
5.1
sp ,
CCCC . E,
, , .
5.2
H 1 (pKa ~25)
pKa 25. ,
NaNH2 CH2=CHLi.
5.3
E pKa (OH) ~15
pKa CCH (~25), , . , CH3Li
A A A
255
C C Li 2 eq CH3Li HO
LiO
C C H
1 eq CH3Li
LiO
5.4
Br
H
Br2
H
NaNH2
H
C
H
H
C
H
2 KOH
CH2Br
H
C
H
CH3CH2Br
Na
CH2CH3
5.5
O 2
H3C C C H
H+
+
H3C C C
H+
H
H2O
HO
H
+
H3C
C C
H3C
+
C C H
H3C
O
C
CH2H
5.6
) . H H3O+/HgSO4
Markovnikov. ,
2,
COH . E,
,
3.
H3C C C CH2CH3
H3O+
HgSO4
H3CH2C
O
C
CH2CH3
+ H3C
O
C
CH2CH2CH3
) . H . E, K>1, G<0.
C C H
O , M O A
256
) .
.
OHC
O3
Zn/CH3COOH
COOH
OHC
5.7
)
CH3CH2CH2CH3
H2/Pd
+
H3O /HgSO4
1 eq HCl
H3C
O
C
CH2CH3
Cl
H3CcCaCcCH3
H2/Pd/CaCO3
2 eq HCl
CH3
H3C
H3C
CH3
CH3CH2CCl2CH3
CH3
Na/NH3
O3
H3C
CH3COOH
5.8
H C C H
NaNH2
NaNH2
H C C Na
CH3CH2CH2Br
CH3CH2CH2Br
H3CH2CH2C C C Na
H3CH2CH2C C C CH2CH2CH3
O3
H2
Lindlar
H3CH2CH2C C C H
H3CH2CH2C
CH2CH2CH3
Zn/CH3COOH
CH3CH2CH2CHO
A A A
H C C H
NaNH2
H3CH2C C C Na
H C C Na
CH3CH2Br
257
CH3CH2Br
NaNH2
H3CH2C C C H
H3CH2C C C CH2CH3
2 H2
Pd
CH3CH2CH2CH2CH2CH3
Br
H C C H
NaNH2
C C H
H C C Na
H2
OH
H3O+
Lindlar
6.1
E 1,3
1,4,
.
H1,4- > H1,3-
H1,3-
H1,4-
6.2
:
Cl
Cl
OH
2 KOH
H+
HO
6.3
) . M A
, B. E, A B.
O , M O A
258
CH2
CH2
CH2
CH2
CH2
) . K H+ 1,3
, Br .
K H+ 5,51,3,
, .
H+
H+
+
+
+
Br
Br-
Br-
H3C CH3
H3C
CH3
Br-
H3C CH3
Br-
Br
Br
Br
T
H3C CH3
H3C CH3
6.4
. E,
1,4 ( ) 1,2 ( ).
A A A
259
6.5
O
+ O
O
O
O
O
CN
CN
6.6
F2C=CF2,
(F), .
F
F
+
F
F
F
C C
F
7.1
) 2,63
) 1I2
) 1,42
7.2
H 1 1 HCl SOCl2.
Cl
SOCl2
OH
HCl
Cl
7.3
()
CH2CN
()
H3CH2CH2C C C H
()
CH3CH2CH2NH2
()
CH3CH2CH2OCH3
O , M O A
260
7.4
,
,
, trans .
KOH
Br
KOH
Br
7.5
) . T A , B . SN2,
, .
) . T CN CH3COO,
pKa HCN pKa CH3COOH ( 7.4.3).
) . SN2 , . H :
(S)
H3C
H3CH2C
C Br
NaCN
H3C
H
C CN
H3CH2C
(R)
) . T I Cl,
I Cl.
) . T CH3CN , (Na+). E, (CN)
.
) . H CH3OH
, .
A A A
261
7.6
) . SN1,
, .
) . E
SN2. SN1,
.
) . E SN1, (CH3COO OH)
. K .
) . ,
SN1 SN2 . E,
.
) . H
SN1,
SN2. ,
SN1.
7.7
) . T 2 1, SN2 .
E, E2 2.
) .
D
D
H
H
Br
CH3
H
CH3
CH3
CH3
DBr
H
C C
H3C
CH3
Br
cis2, Br
O , M O A
262
D H, DBr.
) . T I , . E,
SN2,
E2.
) . T Br F. E,
14, 41.
B
Br
HBr
7.8
T B,
.
7.9
K E1, , , . ( ),
11 (
Saytzef).
B
Cl
H
H
CH3 H
E1
Cl
H
CH3
H
H
CH3
H
H
8.1
) A
) I
) M
.
K
H
H
H3C
B
A.

H3C
A A A
263
8.2
K
28,6 kcal/mol. E , 1,3,5,
3 28,6 = 85,8 kcal/mol. H
85,849,8 = 36 kcal/mol
1,3,5 36 kcal/mol. H .
1,3,5-
( )
+ 3H2
3H2 +
36 kcal
-85,8 kcal/mol
-49,8 kcal/mol
8.3
1,3,5,7
, , .
:
E,
: 4 28,6 = 114,4 kcal/mol.
O , M O A
264
8.4
+{
G +
H
E
+ E+
E
+ H+
8.5
A , , .
CH3
H3C C CH2 AlCl4

+
CH3
CH3
H3C C CH2Cl + AlCl3
CH3
CH3
CH3
C CH2CH3
CH3
H+
H3C + CH3
C C H
H3C
H
8.6
H NH2
,
, . A, CN ,

, :
A A A
265
+
NH2
+
NH2
NH2
+
NH2
C N
C N
C N
C N
+
8.7
.
Cl
H3C
NO2
NO2
H3C
OH
*
8.8
H A
,
. A,
B ,
,
CN.
CN
+
CN
+
H
E
H
E
+
E+
E+
+
+
A
H
CN
CN
+
B
H
E
H
E
CN
E
H
E E+
O , M O A
266
3
2 4. K ,
2 4, ,
.
8.9
O
Cl
CH2CH2CH2COCl
E
Friedel-Crafts
AlCl3
O
A
8.10
CH3COCl
CH3
H3C C Cl
CH3
AlCl3
AlCl3
O
CH3
CH3
H3C C
CH3
Zn-Hg
HCl
CH2CH3
CH3
H3C C
CH3
CH3COCl
KMnO4
O Zn-Hg
AlCl3
Br
NaOH
C CH3
H
HCl
CH2CH3
NBS
ROOR
A
1.1
2p
2s
1s
2p
1s
M BF3
Y
3 T sp2
T (Z = 5) 2p (1s2,
2s2, 2p1). M 2s 2p
s p
sp2 . BF3 sp2 2p F. K , BF3
FBF, 120.
1.2
T Be : 1s2, 2s2.
2s 2p,
s p sp . T Be sp
Cl. K , BeCl2
, ClBeCl 180.
1s
2p
2s
Be
Cl
2p
1s
M BeCl2
Y
2 T sp
120
O , M O A
268
1.3
T A
B, .
H +
O H +
H
O
H
+
:
Y
A
E :
X
B

:
NH2
H2N
NH2
NH2
2.1
11,
(Br) . M
2.3,
0,25 kcal/mol. 1tert1
3,6 kcal/mol.
Br
F
Br
Go = -0,25 kcal/mol
F
C(CH3)3
CH3
C(CH3)3
Go = -3,6 kcal/mol
CH3
4.1
K
, , , O2, . T
269
2 : cis2 trans2. K
4 CO2 4 H2O.
. E , cis2, . ( , E 2.7.)
Hocis
E
cis2
E
trans2
Hotrans
Hocis
Ho
trans
4 CO2 + 4 H2O
4.2
, D2 ,
, . T
R,S S,R, , ( E 3.3).
D
COOH
H
COOH
COOH
H
D2
COOH
M
cis
COOH
D
COOH
A, (trans) S,S
R,R, . E,
D2 (
RR/SS ).
O , M O A
270
H
COOH
HOOC
E
R,R S,S
HOOC
D2
COOH
D
H
HOOC

trans
COOH
E D2 ,

. , D2 cis R,S, R,R S,S.
D2
D
COOH
D2
H
H
COOH
COOH
COOH
(R,R)
COOH
H
(S,S)
HOOC
D2
HOOC
COOH
(R,S)
H
D
E , ! ,
3 .
4.3
) A, ,
( ), B,
.
) E, B BH2 .
271
H3C +
C
H
H
H
C H
H
B
H
H
B
C
H
CH3
B H
H
5.1
H H+ . E
, ( I )
.
Br
R
C
R
T Br -I .

{.
E { X +I ,

{{.
R
X C
R
E, , .
H
R
C C
R
H
R C C R
H X
H+
X
H
R C C R
H X
H
R C C R
H X
XH X
R C C R
H X

H
R C C R
H X
XX H
R C C R
H X

A
, 8.7.2. A
, ! .
O , M O A
272
8.1
2 ,
, , Hckel. , ,
.
+
A (2 e)
+
+
A (6 e)
A (6 e)
A (3 e)
A (4 e)
.
8.2
K ( 4.6.2
4.6.3) . T FriedelCrafts
. , 22 H+
, .
H
H+
+
H+
H2C C
CH3
CH3
H+
H +
CH3
H2C C
CH3
H+
CH3
C CH3
CH3
273
8.3
A E+ , , N. E,
(3).
+
+
H
E
H
E
H
E
N
+
E+
H
E
H
E
H
E
N
+
A
A
2.1
Cl
Cl2
Cl
Cl
Cl
Cl2
h
Cl
Cl2
Cl
+
Cl
2.2
(CH3)3CH
> CH3CH2CH2CH3
> CH4
2.3
CH3
CH3
H
CH3
H
CH3
H
2.4
Cl
Cl
Cl
Na
Na
Cl
2.5
(CH3)3CH
+ Br2
Br2
h
(CH3)3CBr
Br (A)
Li
(CH3)3CLi
(A)
CH3
C CH3
CH3
275
3.1
A. B. T . T .
3.2
OH
O
HO
H
HO
O
H
S
CH2OH
3.3
H Cl
Cl2
H Cl
Cl
Cl
H Cl
Cl
+
+
H
H Cl
+
Cl
H Cl H Cl
H ClCl H
Cl
H Cl
+
Cl
4.1
A = 3,3
=
B = 1 2
= 1,2
T = 41
E =
Z = 1
4.2
OH
H+
KOH
I
H2O
OH
: CH2
Br2
H2O
Br
O , M O A
276
5.1
H3CH2C C C H
H3CH2C C C CH3
: CH2
H3CH2C
CH3
H2O2/OH-
H2
C C CH2CH3
H C C H
BH3
CH3
H3CH2C
Pd
CH3CH2CH2CH2OH
5.2
Na
Cl
Br2
Cl
Br
h
1 eq HCl
H C C Na
Br
C C H
Cl
7.1
> > .
7.2
> > .
7.3
H D
CN
CN
I
I
Br
H D
CN
Br
D H
Br
CN
277
8.1
H
Br
C
H3C
CH2CH3
H
C+
H3C
CH2CH3
AlCl3
(S)
H
H3C *C CH2CH3
50% R + 50% S
H+
8.2
Br2
Br
Mg
MgBr
FeBr3
D2O
8.3
.

E+
E
+
+
E H
8.4
Cl
Ph
AlCl3
CH3
CH3
AlCl4
H+
AlCl4
+
CH3
+ H
CH3
E
A
156
A FriedelCrafts
221
221
A FriedelCrafts
220
232
89
68
31, 71
173
173
175
91, 186, 234
219
141
94
A Clemmensen
233
A WolffKishner
233
84
A Walden
191
231
214
46
44
44
A E1
204
A E2
200
A DielsAlder
178
A Wurtz
90
A SN1
196
A SN2
190
O , M O A
280
A Grignard
89
AMarkovnikov
143
A (a)
84
222
172
45
188
194
211, 214
214
122
108
17
133
132, 158
B BrnstedLowry
37
B Lewis
40
235
158
98
Cis
88, 129
129
79
32
22
22
C (2o)
66
73
72
83
76, 201
EYPETHPIO
281
gauche
76
scis
179
strans
179
86
114
178
194
33
146
Kekul
20
Lewis
20
36
van der Waals
31, 71
112
73
92
107
54
50
E Gibbs, G
53
E , D
30
54
222
50
34
194, 199
156
46
28
18
47, 216
O , M O A
282
40
177
157
140
19
I (e)
84
30
56
K Hckel
214
K Markovnikov
136
K Saytzef
189
K CahnIngoldPrelog
109, 130
144
137
K Lindlar
160
K CC
82
177
42
115
116
211
53
M Gibbs, G
49
M , H
50
M , S
50
45
149
46
230
218
147
EYPETHPIO
283
147, 162
46
19
46
66
O BrnstedLowry
37
O Lewis
40
112
211
211
47, 178
46
29
229
112
Fischer
117
Newman
73
223
1,2 1,4
174
141
134
194
C (1o)
66
187
47, 188
113
218
65, 87, 119
108
76
73
O , M O A
284
171
65, 119
35
73
162
T C (4o)
66
Trans
88, 129
27, 155
T C (3o)
66
Y sp3
23
Y sp
25
Y sp
26
143
89, 134, 159, 233
42
107
96

Fye 30 A

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Fye 30 A

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O , M

OYE TI YIKE EITHME

4.6.5 ................................................................................ 141

A DielsAlder ................................................................................................... 178

A . M SN2 ...... 190

A . M SN1 ...... 196

8.10 A ................................................................................. 233

Y sp, sp2 sp3

Van der Waals

H ( ) , (1s, 2s, 2p,

1s2, 2s2, 2p5

1s2, 2s2, 2p2

1s2, 2s2, 2p6, 3s1

1s2, 2s2, 2p3

1s2, 2s2, 2p6, 3s2, 3p2

1s2, 2s2, 2p4

1s2, 2s2, 2p6, 3s2, 3p6

H (1s2, 2s2, 2p2) 2

T sp3 , . H ( ). , (CH4) sp3 1s . O

C=C, C=N C=O,

H , AB, A B , , .. HH, CH3CH3, BrBr. ,

van der Waals:

M , Lewis Kekul. , , CH3COO. Kekul -

, HCl , H2O , Cl H3O+. T

NH3 (pKa ~ 32). A, (OH)

BrnstedLowry, Lewis H2O,

RI, RBr, RCl, RF

G , Keq >> 1, . , G 4 kcal/mol, Keq ~ 103,

190 kcal/mol, H = 10 kcal/mol, .

K H3CH (D = 104 kcal/mol)

H2C= CH2 + HBr

A van der Waals

O (1o), (2o), (3o) (4o) ,

) H gauche 1,2 (ClCH2CH2Cl)

H 27,6 kcal/mol ( 2.2).

, (axial, a) (equatorial, e). T , , -

) . (RLi) (R'X), R'R. O CLi Li .

1.3 (E 1.6) (D) (1) , (2) (3). ,

K , 1 2 43/57. , 75/25 ( 6/2), , 1, , 2.

, 2R,3S 180, 2S,3R. A, 2R,3R/2S,3S

H . A , trans cis (E 4.4). H cis trans , .. cis trans2, ,

K (.. H+/H2O HBr), ,

pKa . H CH CCH > C=CH > CCH.

E 1,2 (. 4.6.4), 1,2 , :

, . , Br2 1,3, : 3,41, 1,2, 1,42, 1,4. T

BrCH2 - CH(Br) - CH = CH2

BrCH2 -CH = CH - CH2Br

HCH2 - CH(Br) - CH = CH2

HCH2 -CH = CH - CH2Br

T 1,2 HBr 1,3 Markovnikov, Br

H C CH=CH2 > H C CH=CH2 H3C C

1,2 1,4 , , 1,4 .

) (HX) . H 4.6.2 4.6.8. X

O , .. H2O, SN2, , . A, , , .. CH3CN (CH3)2S=O,

K , , (. 4.6.2). , H2O SN1, tert-

A: O . H CX : CF > CCl > CBr > CI.

+Br .... FeBr

A, OH, NH2, NHCOCH3

NO2, CN, COOH, CHO,

8.1 , (OH), (NH2), . O

) B (1s2, 2s2, 2s1),

) Cl (1s2, 2s2, 2p6, 3s2, 3p5).

) H3CMg+CH3, ) H3C+OH, ) H3C+NH2.