Взаимодействие перфторбензоциклобутена и его перфторалкил- и пентафторфенилпроизводных с CO в среде SbF5

1.

Взаимодействие перфторбензоциклобутена и его
перфторалкил- и пентафторфенилпроизводных
с CO в среде SbF5
Я. В. Зонов, В. М. Карпов, В. Е. Платонов
Новосибирский институт органической химии
им. Н. Н. Ворожцова СО РАН

2.

2
R OH
êèñëî òà
R Hal
+ CO
R
+
R CO
HX
R COX
+
CO
RF
RF
+
CO
í åèçâåñòí î
àëêåí û
CH4
CO
HF/SbF5
CH3
+
CO
H2O
CH3COOH
CF3COF
C2H5OH
1) CO, HF/SbF5
2) H2O
- CO
1) CO, SbF5
Cl
CF4
C2H5COOH
CF2COF
2) H2O
SbF5
F
COOH
SbF5
- CO
CF3
F

3.

3
F
CFCF3
C2F5
+
C2F5 CF2
C2F5 CF3
SbF5
F F
F
F
CF2
F
+
CF2
CF3
[1]
CF3
[1] В.М. Карпов и др.
Изв. АН СССР (1990) 1114
R
F
R
SbF5
F
R'
R"
F
R
CO
CO
+
R'
R
+
CO
F
R"
F
R'
R"
+
CR'R"
A
R
F
F
CO
SbF5
R = F, AlkF, C6F5
?
...

4.

F
F
+ CO
F
7
F
+
CO
_
+ F-
COF
+
CO
F
F
8
9
SbF5
F
F
o
20 C
1
F
F
F
O
+
CF2
F
COF
F
O
CF3
F
+ O
4 O
(15%)
CH2COOH
F
5
(49%)
O
+
F
F
+
F
COOH
6
(45%)
4 O
(6%)
F
O
4 O
CF3
COOH
F
SbF5
70oC
O
H2O
F
O
CF3
F
3 F
(8%)
2
(ñî äåðæàí èå 77%)
4
2
F
F
F
F
10
+
CO
CO, SbF5
F
+
CO
CO
+
CO
COF
O

5.

5
CF3
+
F
F
CO
...
SbF5
1) CO, SbF5,
CF3
20oC
2) H2O
CF3
F
F
COOH
CF3
F
F
O
+
CH2COOH
F
COOH
COOH
F
1) CO, SbF5,
20oC
2) H2O
F
SbF5
CF3
F
CF3
CF3
F
CH2COOH
F
+
CO
...
F
O
+
F
COOH
CF3

6.

6
COOH
F
F
F
CF3
H2O
+
CO
CF3
F
F
CO, SbF5
20oC
CF3
SbF5
CF2
F
20oC
CF3
_
+ F-
F
+
F
CF3
CO
F
F
+
CO
CF3
CO
CF3
F
+
CF2
F
+ O
68
:
12 F
32 (÷åðåç 6 ÷)
25
:
75 (÷åðåç 24 ÷)
11
SbF5
F

7.

F
F
CF2CF3
CO, SbF5
20oC
+
CO
CFCF3
F
7
COOH
H2O
CFCF3
F
CF3
CF3
13 (E:Z = 92:8)
COOH
CF(CF3)2
F
F
1) CO, SbF5,
20oC
2) H2O
CF3
F
CF3
14
15
âû õî ä 53%
C6F5
F
CF3
F
C6F5
CO, SbF5
20-70oC
C6F5
F
F
+ O
16 F
H2O
F
F
O
17 O
âû õî ä 70%

8.

F
F
CF2CF3
CF3
;
F
F
CF2CF3
CF2CF3
CO, SbF5
ðåàêöèÿ í å èäåò

9.

F
1) CO, SbF5, 20oC
F
O
F
2) CH3OH
CF2CF3
CF3CF2
CF2CF3
F
F
CO, SbF5
20oC
O
F
CF3CF2 COF
18
CO SbF5
CO F-
+
CO
CF3CF2
+
F
CF3CF2
COOCH3
CF3CF2 COOCH3
CF3CF2 COF
CF2CF3
CF3CF2
9
CF3 COOCH3
CF3
O
F
X
CF3CF2
X = F èëè COF
CF3CF2
F
CO
+
CF3CF2
X
X
CH3OH
F
CF3CF2
O
COOCH3
âû õî ä 40%

10.

CF(CF3)2
F
F
CO, SbF5
o
CF(CF3)2
F
F
H2O
CO, SbF5
O
F
O
(CF3)2CF COF
(CF3)2CF COF
21
o
CF3
O
F
20 C
20
C6F5
CF(CF3)2
CF(CF3)2
+
+
F
22
âû õî ä 65%
C6F5
C6F5
O
HF
F
F
O
50 C
F CF3
23
CF3
24
âû õî ä 70%
10

11.

R
F
F
CO, SbF5
F
F
70oC
R
F
CH3OH
F
+ O
R = CF2CF3
CF(CF3)2
F
1) CO, SbF5, 70oC
F
2) CH3OH
CF3
CF3
CF2CF3
F
F
CH3O
O
F
+
F
CH3O
CF3
2 : 1
C6F5
C6F5
F
F
CF3
1) CO, SbF5, 75oC
2) CH3OH
O
CH3O R
âû õî ä 53%
79%
R
CF2CF3
11
R
R
F
F
O
CH3O CF3
25
O
CF2CF3

12.

12
R
F
CO
(2 ì î ëü)
F
SbF5
+
CO
R
F
F
R
O X = F, COF
F
O
R
R = F, CF3
AlkF
F
F
C6F5
F
SbF5
R2
CF3
F
R = AlkF, C6F5
F
R
CO
(1 ì î ëü)
SbF5
C6F5
CO
(1 ì î ëü)
20oC
R
R1
F
X
CO
(1-3 ì î ëü)
SbF5
+
CO
CO
(1 ì î ëü)
SbF5
F
X
70oC
R
F
F
+ O
F
F
F
+ O
R

13.

13

14.

R
CO
+
CO
F
R
X
- CO
R
+
CO
O
F
R
R
+
O
F
F
O
+
X
R
X = F èëè COF
X
R
R
+
CO
R
X
F
F-
C
- CO
R
R
X
F
F
O
X
R

15.

+
CO
CO
CF2
+ FCF2 _
F
F
F
O
F
O
+
+
CF2
F
F
F
O
+
CO
O
F
O
_
+ F+
CO
CF3
F
F
O
4 O
-F-
SbF5
o
70 C
COF
CF3
F F-
F
F
O
2
(ñî äåðæàí èå 80%)
F
+ O
3 F
(9%)
F-
-
F
F
-F
4 O
(11%)
O

16.

C6F5
F
F
31
SbF5
F
+
F
C6F5
CO
F
C6F5
+
CO
F
C6F5
C
F
C
+
CF2
C6F5
F
O
F
+ O
32 F

17.

JFF = 2 Hz
COX
F
CF3
C C
F
F
CF3
E
JFF = 3-3.5 Hz
COX
F
F
C C
CF3
F
CF3
JFF = 2 Hz
Z