1
4 8 Pa g e 4 o f 9
J. Chem. Sci. ( 202 0)13 2: 148
(
p pm ) = 7 .7 7 - 7. 8 4 ( 4H , m , A r) , 6. 03 -6 .0 6 ( 1H , m , H C =C H) , (p pm ) = 7. 9 6 (1 H, d, J = 7. 3 Hz, Ar ), 7. 78 ( 1H, d ,
5
1
. 8 5 -5 .8 6 (1 H , m , H C= C H ), 5. 52 -5 .5 3 ( 1H , m , H- C -O) , J = 6. 4 Hz, Ar ), 7. 36- 7 . 40 (1 H, m , Ar ), 7. 13 ( 1H, d ,
1
3
. 8 5 -2 .2 0 (m , 6 H, CH ) .; C N M R ( 10 0 MH z, CD C l ): d
C
J = 6. 2 Hz, Ar ), 6. 23- 6 . 25 (1 H, m , HC =C H) , 5 .6 2 -5 . 68
2
3
(
p pm ) = 1 6 5 .8 , 1 3 7 .7 , 13 3. 1, 13 1. 1, 13 0. 3, 12 5. 5, 100 .5 , (4 H, m , HC =C H and H- C- O ), 2. 83- 2 . 88 (1 H , m , CH ) ,
2
1
3
6
9 . 0, 2 8 .4 , 2 4 . 9 . 1 8 .9 .; m /z ( %) : 32 8 ( 0.5 , M) , 24 8 (6 ), 231 2. 53- 2 . 60 (3 H, m , C H ), 2. 15- 2 . 35 (2 H, m , C H ). ; C N M R
2 2
(
1 1), 1 2 7 (1 7 ), 1 1 1 ( 25 ), 97 ( 61 ), 85 ( 71 ), 57 ( 10 0) .
(7 5 MHz , C DC l ): d (p pm ) = 166 .0 , 141 .2 , 135 .4, 1 32 . 6,
C
3
1
30 .9 , 129 .8 , 1 29. 6, 129 .5 , 128 .7 , 127 .9 , 12 5. 1, 94 . 1, 7 4. 0 ,
33. 9, 28. 0, 27. 9. ; m / z (% ) : 354 (0 .7, M) , 248 (3 4) , 22 8 ( 10 ) ,
27 (1 9), 122 (1 00) , 5 7 (6 5) , 54 (1 00).
2
. 3 e Cyclooct-2-en-1-yl 2-iodobenzoate 6a:
1
2.3 h Cycloocta-2,6-dien-1-yl 4-iodobenzoate 7c:
-
1
Re d o i l .; FT -IR ( K Br ) ( m /c m ) : 3 07 2, 29 6 7, 171 7,
m ax
1
1
6 4 4 , 4 7 5 .; H NM R ( 30 0 MH z, CD Cl ) : d ( pp m ) = 7. 98
H
3
(
1 H , d , J = 7 .9 Hz , A r) , 7. 78 -7 .8 1 ( 1H , m , A r ) , 7. 40 (1 H, t ,
J = 7 .6 Hz , Ar ), 7 .1 2- 7 .1 7 ( 1H , m , A r ) , 5. 90 -5 .9 5 (1 H, m ,
HC =C H ), 5 .6 2 - 5. 7 2 ( 2H , m , H C= CH an d H -C -O ) , 2. 88- 2 . 92 172 6, 166 8, 472 .; H NM R (4 00 MH z, C DC l
m, 1 H, C H ), 2 .2 7 -2 .4 0 ( m , 1H , CH ) , 2. 13 -2 .1 7 (m , 4H , (p pm ) = 7. 7 6 7. 84 (4 H, m , Ar ), 6. 21- 6.2 3 (1 H, m , HC =C H) ,
-
1
R e d t o br own oi l .; F T-I R (K B r) ( m
/ cm ): 3072 , 2 95 3,
) : d
m
a
x
1
3
H
(
2
2
3
1
C
H
)
,
1
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H
)
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M
H
z
,
5
.
5
8
-
5
.
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5
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C
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)
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4
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.
8
8
(
1
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m
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(
p
p
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1
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6
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1
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1
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1
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1
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1
3
1
.
1
,
1
3
0
.
6
,
C
H
), 2 . 53-2 .61 (3 H , m , C H
C NMR (1 00 MH z, C DC l
5 6 (0 . 4 , M ), 2 4 8 (1 2 ) , 23 0 ( 6) , 12 7 ( 28 ), 12 4 ( 10 0) , 57 (6 5). 131 .1 , 130 .0 , 1 29. 9, 129 .4 , 128 .9 , 125 .1 , 10 0. 7, 73 . 4, 3 3. 9 ,
8. 0, 27. 9. ; m / z (% ) : 354 (0 .5, M) , 248 (4 3) , 228 (1 2) , 1 27
(2 3), 122 (9 2), 57 (5 2) , 54 (1 00) .
)
,
2
.
2
6
-
2
.
3
5
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2
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,
m
,
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H
)
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;
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5
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8
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3
.
4
.
;
m
/
z
(
%
)
:
3
)
:
d
C
(
p
p
m
)
=
1
6
5
.
5
,
1
3
7
.
7
,
3
2
2
.
3
f
C
y
c
l
o
o
c
t
-
2
-
e
n
-
1
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y
l
2
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i
o
d
o
b
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n
z
o
a
t
e
6
c
:
2
.
3
i
C
y
c
l
o
h
e
x
-
2
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e
n
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1
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y
l
b
e
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:
-
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.
;
F
T
-
I
R
(
K
B
r
)
(
m
/
c
m
)
:
3
0
7
7
,
2
9
5
4
,
m
a
x
-
C ol or l es s oi l .; F T-I R (K Br , cm ): 306 5, 293 9, 1 71 1,
1
1
1
7 2 5 , 1 6 7 5 , 4 5 6 .; H N M R ( 40 0 MH z, CD C l ): dH
3
1
65 3, 149 1, 106 6. ; H NM R (4 00 MH z, C DC l ) : dH
p pm ) = 8. 0 8- 8.1 0 (2 H , m , Ar ), 7. 56- 7 . 60 (1 H, m, Ar ) ,
1
(
p pm ) = 7 .7 7 -7 . 8 3 ( 4H , m , A r) , 5. 91 -5 .9 3 ( 1H, m ,
3
(
HC = CH ), 5 .7 2 - 5 .7 9 ( 1H , m , H C= C H ), 5. 60 -5 .6 4 (1 H , m ,
H- C- O ), 2 .3 1 -2 . 4 0 ( 2H , m , CH ) , 2. 06 -2 .2 0 ( 4H , m, C H ),
7
5
. 45- 7 . 48 (2 H, m , Ar ), 6. 03- 6 . 05 (1 H , m , HC =C H ) , 5 .8 8 -
. 89 (1 H, m , HC =C H) , 5. 54 (1 H, d d, J = 3. 4, 1. 6 Hz , H- C-
2
2
1
3
1
. 4 6- 1 .6 5 (4 H , m , CH ) .; C N M R ( 10 0 MH z, CD C l ): d
C
2
3
1
3
O) , 1. 62- 2 . 16 (6 H , m , C H ). ; C NMR (1 00 MH z, CD Cl 3 ) :
2
(
p pm ) = 1 6 5 .5 , 1 3 7 .7 , 13 1. 1, 13 0. 4, 13 0. 3, 13 0. 1, 100 .5 ,
dC (p pm ) = 166 .2 , 132 .9 , 132 .8 , 130 .8 , 129 .6 , 128 .2, 1 25 . 8,
7
2
3 . 4, 3 5 .1 , 2 8 .4 , 2 6. 4, 25 .9 , 23 .4 .; m /z ( %) : 35 6 ( 0. 6, M) ,
4 8 (1 8 ), 2 3 0 (6 ) , 1 27 ( 27 ) , 12 4 ( 10 0) , 57 ( 73 ).
68. 6, 28. 4, 25. 0, 19. 0. ; m / z (% ): 202 (0 .5, M) , 122 (2 3) , 1 11
(3 7), 97 (5 4), 85 (5 3) , 57 (1 00) .
2 . 3 g Cycloocta-2,6-dien-1-yl 2-iodobenzoate 7a:
3. Results and Discussion
3.1 Catalytic allylic C–H bonds oxidation
(
Kharasch - Sosnovsky reaction)
T
h
a
i
e
s
y
n
t
h
e
e
x
s
c
i
e
s
l
o
o
f
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l
y
l
y
l
i
l
n
c
d
e
e
s
s
s
f
t
r
e
o
r
s 4-9
p
e
a
tert
r
l
f
o
l
r
i
-
m
c
e
C
t
d
i
n
m
o
n
d
d
o
-
-
1
Re d t o b ro wn o i l . ; F T- IR ( K Br ) ( m /c m ) : 30 8 0, 295 9,
e
r
t
e
to
le
i
e
m
th
e
ly
-H
bo
m ax
1
1
7 3 7 , 1 6 5 9 , 4 8 6 .; H N M R ( 30 0 MH z, CD C l ): dH
ox
d
a
t
i
o
n
f
l
k
e
w
it
h
bu
y
l
iod
3