.
, () , , CnH2n-2.
.
: C2H2 H C ≡ C H ,
, , ' s −. , s - -, - . σ-, - , π-. , σ- π-.
, , , . 180. , π-, σ-, .
0,120 ( , 0,154 0,134 ), , , .
, , ( σ-) π- , , , , , , − .
− , -2- .
( ): 22 − , 34 − , 46 − . , ( ): 58 − , 610 − , 712 − ..
, . .
1. . - . .
2. . , ( ):
|
|
→ → .
.. .
, , .
3. ., , , , , , .. , .
, − , . , (2,2-). ( , , − , − ) (. , ). − . − ( (), , ..).
:
CH3 Cl CH3
7 6| 5| 4| 3 2 1
CH3 CH CH C C ≡ C CH3
|
C2H5
4,6--4--5--2
.
:
1. :
)
1 2 3 4 5 1 2 3 4
CH≡C CH2 CH2 CH3 CH≡C CH CH3
|
CH3
-1 3--1
)
1 2 3 4 5 1 2 3 4 5
CH≡C CH2 CH2 CH3 CH3C ≡ C CH2 CH3
-1 -2
) (Hal, - NO2, SO2-OH .)
1 2 3 4 5 1 2 3 4 5
CH ≡ C CH CH2 CH3 CH ≡ C CH2 CH CH3
| |
Cl Cl
3--1 4--1
2. , , .
3. ( )
1 2 3 4 5 1 2 3 4 5
CH ≡ CH CH2 CH2 CH3 CH2=CH CH = CH CH3 CH = CH
-1 1,3- | |
CH2 CH2
\ /
CH2
.
C2H2 C4H6 , C5H8 C15H28 - , C16H30 . , , . . , , . .
6. .
I. ( ).
1. ( Pt, Pd, Ni):
CH ≡ C CH3 + 2 H2 → CH3 CH2 CH3
CH ≡ C CH3 + H H → CH2=CH CH3 I
CH2=CH CH3 + H H → CH3 CH2 CH3 II
2.
CH ≡ C CH3 + 2 Br2 → CHBr2 CBr2 CH3
1 2 3
CH ≡ C CH3 + Br Br → CH = C CH3 I
|
|
| |
Br Br
1,2-
Br Br
1 | 2 | 3
CH = C CH3 + Br Br → CH C CH3 II
| | | |
Br Br Br Br
1,2- 1,1,2,2-
( ).
3. ( : HX ( X Hal, -OH ..) - , X )
CH ≡ C CH3 + 2 HBr → CH3 CBr2 CH3
1 2 3
CH ≡ CH CH3 + H Br → CH2 = C CH3 I
|
Br
2-
Br
1 2 3 1 2 | 3
CH2=CH CH3 + H Br → CH3 CH CH3 II
| |
Br Br
2- 2,2-
4. ( ): , ( . .)
H
Hg+ /
HC ≡ CH + H OH → CH2 = CH → CH3 C
| \\
O H O
Hg+
CH ≡ C CH3 + H OH → CH2 = C CH3 → CH3 C CH3
| ||
O H O
II. .
1.
t
2 C2H2 + 5 O2 () → 4 CO2 + 2 H2O
t
2 C2H2 + 3 O2 () → 4 CO + 2 H2O
t
2 C2H2 + O2 ( ) → 4 C + 2 H2O
; .
2. (KMnO4 , K2Cr2O7 ) .
O O
KMnO4 \\ //
CH ≡ CH + 4 [O] → HO C C OH
()
O O
\\ //
3 CH ≡ CH + 8 KMnO4 + 4 H2O → 3 HO C C OH + 8 KOH + 8 MnO2
, :
O O
\\ //
3HC-1 ≡ C-1H + 8KMn+7O4 → 3KO C+3 C+3 OK + 2KOH + 8Mn+4O2 + 2H2O
C2-1 -8ē → C2+3 3 3C2-2 -24ē → 3C2+3
Mn+7 +3ē → Mn+4 8 8Mn+7 +24ē → 8Mn+4
O
KMnO4 //
CH3 C ≡ C CH3 + 3 [O] + H2O → 2 CH3 C
\
OH
-2
( )
O O
KMnO4 // //
CH3 C ≡CH + 3 [O] + H2O → CH3 C + H C
\ \
OH OH
( ) ( )
KMnO4 ( , ).
III. .
1. ()
kt 1 2 3 4
CH ≡ CH + CH ≡ CH → CH2 = CH C ≡ CH
(-1--3)
2. ()
3 C2H2 → C6H6
3.
t0, kt, P
+ CH2≡CH2 + CH2≡CH2 + → -CH2 = CH2 CH2 = CH2-
t0, kt, P
n CH ≡ CH → ( CH = CH )n
n
t0, kt, P
n CH3 C ≡ CH → ( C = CH )n
|
CH3
() ()
IV. ( H, sp - ). , sp - , ( ≡CH), . .
1.
|
|
2 CH ≡ CH + 2 Na → 2 CH ≡ CNa +H2 I
2 CH ≡ CNa + 2 Na → 2 CNa ≡ CNa + H2 II
:
CH ≡ CH + NaNH2 → 2 CH ≡ CNa +NH3↑
2. (I)
CH3 C ≡ CH + [Cu(NH3)2]Cl → CH3 C ≡ CCu↓ + HCl + 2 NH3↑
(I)
CH3 C ≡ C CH3 + [Cu(NH3)2]Cl →
. , !
3. (I)
CH3 C ≡ CH + [Ag(NH3)2]OH → CH3 C ≡ CAg↓ + H2O + NH3↑
(I)
CH3 C ≡ C CH3 + [Ag(NH3)2]O →
. , !
V. ( ).
. - KOH; 170
CH ≡ C CH2 CH3 -------------------------→ CH3 C ≡ C CH3
-1 -2
() ()
.
I.
1.
. :
1000C
2 CH4 ---------→ CH ≡ CH + 3 H2
1200C
CH2 = CH2 ----------→ CH ≡ CH + 2 H2
2.
. ( .) (K, Mg)
CaC2 + 2 H2O → C2H2↑ + Ca(OH)2
C H OH C H OH
Ca + → + Ca
C H OH C H OH
II.
1. :
H Br
| | t
CH3 CH2 C C CH3 + 2 Na OH → CH3 CH2 C ≡ C CH3 + 2 Na Br + 2 H OH
| |
Br H
2,3- -2
H Br
| | t
CH3 CH2 C CH + 2 Na OH → CH3 CH2 C ≡ CH + 2 Na Br + 2 H OH
| |
H Br
1,1- -1
()
2.
CH3 C ≡ C Na + Br CH2 CH3 → CH3 C ≡ C CH2 CH3 + NaBr
(-2)
.
1,2-
(CH3COOC2H5) (CH2Cl CH2Cl)
(HOOC COOH)
(CH3COOH) CH ≡ CH
(CH3COOCH = CH2)
( ) (CH2 = CH C ≡ CH)
(CH3CHO)
( ) (2--1,3) CHCl = CH2
(C2H5OH) (CH2 = CCl CH = CH2)
,
: ( )
1. ?
2. (, , )?
3. ?
|
|
4. ?
5. ? .
6. ? .
7. ? .
8. ? .
9. ? .
10. ?
:
- ( 15-), . ., --, 2006
- . ., . ., . ., . . 10 : . ( ), , 2005
- . ., . . 10: ( 10 ), , 1991
- . ., . . ( ), , 1982
- . 1 ( ) . . ( ), , 2004