+
,
!"#
+
$
% &'
%&'(
) '
"*
) '
"*
,
+
.
/
1
+
,
) '
+
"*
,
-
(
%& '0 (
% &'
1$''% 2 1 '%
1$''1 2 %&'
3
) '
"*
2
+
,
α"
.
"
,
"
1 4 "$%&"$5%0"6'&
1 4 "$%&"$'"$5%#
1 4 "$%&"$'"$5%0"7
1 4 "$%&"$'"$5%0"
"
"
"
"
) '
+
"*
,
%& '0
%$
!
!" !
,
!"
'%
'%
'
%
2
18'%
1
1
1
'%
'%
'%
1
'%
%'
18
'
'%
'%&
'
!#
18
"%&'
"%2
1
1
'18
'18
) '
"*
3
+
,
(
6"
:
"
9'% (
(
"
6&
'
'
1
2 $%&4646
2 6&
1
'%
'$%!
) '
+
"*
,
$ %
!#
(
#
;
(
<
+
(
6&
) '
"*
4
+
,
,
&
# *
) '
+
,
'
-
<
6
(
9
1 '%
(
1 '"
'
1
"
'18
:
'%"
"
1$''
'"
'
1
"*
'%
'%
2 18'"
1
'18
'%
"
1$'' 2 18'%
-
%2
) '
"*
5
+
,
(
(
,
$
/
*
6"
*
$
!(#"
) '
+
(
"*
,
)
%
*
(
6"
(
+
-
<
O
R
O
+ CH3OH
OR'
R
+
R'OH
OCH3
) '
"*
6
+
,
1
'$%!
'
2
2
1
2 ,6%!
'
"%
6%!
1
"
2 $%!'
1
6%&
'$%!
6%&
'$%!
'
'
1
2 %&6"$%&"
1
H
"
'
'
"
2 $%!'
6%"$%&"
'$%!
) '
+
$&%#
"*
,
7 2 $5%#6%&
$5%#6%
7 2 $&%5
6%$5%#
& $5%#6%
7 21$''18
1
6%$5%# 2 18'
'
7
7
'
& %$
$5%#6%&=%$ 2
7 $ 21
6%$5%#
) '
"*
7
+
,
,
-
".
!(#"
NO2
O
R
NO2
∆( >
+
O
Cl-CO
R
OR'
+
R'O-CO
Cl
NO2
NO2
) '
"*
/
(
(
*
0
'
$
1
O
OH O
C=O + NH2-NH-Ph
C-NH-NH-Ph
) '
"*
8
*
/
%
$
%
%$
'18
%$
1"$%' 2 & 18'%
%&' 2
1
$%
'18
1
'
'$%!
$ 2 %"$ '$%!
%"$''$%! 2 1
!
$
1
1
'$%!
:
) '
*
"*
,
'%
$
(
$
0"#
$
%&'(
) '
"*
9
*
,
&+
/2
#+
3
"+
4+
%
.+
5+
) '
*
"*
,
,
& 1'% 2 & 6 "?& 1'6 2 !#
/2
-
9'%
$
(
9
@
&
1'% 2 9'%
% & ' 2 1'9
1'9 2 $
6% 0 & ' 0
%2
9
%
9
&
2
'!
'1
'1
) '
"*
10
*
,
3
/
(
:
6
!
#
-
(
%$
ROH
ZnCl2
+ HCl
RCl
+ H2O
6A
6&
ROH2
R + H2O
ROH2 + X
R+X
[X ...R...O H2]
RX + H2 O
RX
) '
*
3
%
&+
#+
%
"*
,
)
75
)
5
*
-
(
%8
<
*
(
"+
-
B# (
4+
-
C
,
?
??
) '
"*
11
*
,
-
<
*
!
!"
1
!"
!
%
(
9
&(0"
'0(
(
*
*
D$ &
AE ,
&E !E ,
:
) '
*
"*
,
1
(
'%
ROCOCH3 + CH3COOH
ROH + (CH3CO)2O
%
"
$%!$5%0 '&$
-".
!(#"
(
'"
'
2 1'%
*
$
-
*
%
$
2
'%1
2
'%
*
'
$
2 %$
*
'1
'1
) '
"*
12
*
,
*
"
!"
( !(#"
(
) '
*
"*
,
"
!"
(
&
A
&(
FG"F#H
:
O
COOH
O
+ ROH
COOR
+
COOR
NO2
O
COOH
NO2
resa: 90-95%
NO2
resa: 5-10%
) '
"*
13
*
,
(
(
N
Ar
O + ROH
C
N
O
O
O
Ar
Ar
C
Ar
N
OR
NH
OR
OR
H
H
%&' :
$'& /
6"6&"
O
Ar
N
C
Ar-NH
O + ArNH2
NH-Ar
) '
)
"*
,
.
'%
$ I
6 '%
%&'(
$'&
.
%&'
(
%&'(
) '
"*
14
)
,
,
&+
"
3
#+
%
"+
4+
) '
)
,
"*
,
"
) $!
'%
"
(
)
222
"
) '
"*
15
)
,
3
J
K
%& '0
6 6'&
<
NaNO2
OH
O
N
OH
HON
O
H+
O
N
- H2O
H2SO4
chinonossima
fenolo
HO
N
OH
H2SO4
verde
O
blu
O
N
O Na
NaOH
N
indofenolo
) '
)
OH
"*
,
%
(
-
6 '%
:
J
J
K
K
) '
"*
16
)
,
%& '0
(
HO
OH
(
6 '%
HO
OH
H2SO4
o ZnCl2
O
O
HO
C
NaOH
O
condensazione
- H2O
O
COO
Na
O
O
7
2
)
A *
& 7
! "/
3
) '
"*
) '
"*
,
( "6
"
( !(#"
#4 0
17
)
,
1
* '%
%!$'$"62
$%!$' &' 2
6
2 $%!$''%
6
-%
".
'"
'
"
*
2 * '$'$%!
2 '
'
*
$
"
'
$ 2*
'
$
-
"7
J
K
,
A 6
!
%$
L&
'%L0
) '
)
"*
,
%
'
'
* '% 2 $ "
$%!
%$ 2 * '"
$%!
'
'
#4
'&6
"
'&6
2
*' 2 6 2$
6'&
6 $ 2*'
6'&
%
"
' 2 %&$
$''%
'"$%&"$''% 2 $ "
$
) '
"*
18
*
,
-
(
-
-
AE( &E
5
?5
!E
%
$
%&'(
-
%&'(
%&'
) '
*
"*
,
&+
#+
!
%
"+
4+ ,
)
"
.+
%
5+
%
9+
:+ ,
*
%
;+ (
&<+ ,
) '
"*
19
*
,
+M
%$ G(A 6
+
+M
&6
%$
) '
*
"*
,
!
/
(
-
"7
6 '%
"
(
N
O
RNH2
+
O
NaOH
Cl
S
CH3
R
HN
O
NH + Cl
R'
CH3
+ HCl
O
O
R
S
S
O
CH3
NaOH
O
R
N
R'
S
CH3
+ HCl
O
) '
"*
20
*
,
!
/
6 '%
,
A
%
,
L
6 '%
(
&
,
O
!
,
) '
*
"*
,
!
(
,
6
<
6
L
(
6
(
(
) '
"*
21
*
,
%
+
&=
%& '0
β"
/
6 6'&
GE$
6 '%
) '
*
,
,
+
'
$
* 6'!
"*
%&
&
*
& 1$%&6%& 2 $
/ C
P
&
(
2 1$%&6%!2
1"%&$"%6
&
"
* 6'!
2 1$%&6%!2 6'!"
1"%&$"%6
*
&
1"%&$"%6
*
& 1"$%&"64$4 2 *
) '
&
2 %&
"*
22
*
,
"
+
AE
AE( &E
(
&E
(
(
!E -
!"6
!E
'
'
$'6%1
1"6%& 2
$''%
∆( A#G
"%&'
'
$''%
'
6'&
6'&
6'&
'
6'&
'
6' &
'
'
6'&
'
'
1"6%" 18 2
6"1
$'6%1
'
6118
'%
'%
6118
6'&
'
) '
*
"*
,
"
AE( &E
/
%$
!E
(
!E 6
(
:
!E
A#G E$
!"
*
6 %$'!
&E(
AE
) '
"*
23
*
,
%
#>, )
*.
? %
)
'
'
'
*
/ &=(
%
6 %$'!
/ #=(
) '
*
"*
,
,
%
&=
#=
%$ 56
"
&=
#=
&=
#=
$&%#'%
,
/,
/,
"=,
) '
"*
24
*
,
(
+
,
-
AE
AE
!# !#
- *
%6'&
6&
!
!# !
#
!#
#
AE
%6'&
!#
*
!
≡
#
(
!#
(
) '
*
"*
,
(
%6'&
&E
6"
!
- *
- *
(
!
%&'
@
@
!#
!E
!E
"
"
6 '% :
* "6 $%!
&
2 '46"'%
%$
'6
2
6% $%!
&
2 $ " 2 % &'
6 '%
'6
6 $%!
&
26 $ 2
% &'
) '
"*
25
*
,
-
,
AE
$%$ !
9'%
*
6%&
% $
%
1
6,
6
2 !9$ 2 !%&'
$
$
$
%',
*
2 $%$ ! 2 !9'%
" %&'
$
$
$
$
%
$
$$ &
1
$"
2
6
$
%
,$$ & 2 $ "
$
" %$
'%
%
*
"
2
1
6
$
%
$
"
" %$
'%
"
1
6
) '
"*
) '
"*
$
,
0
&+ 7
#+ !(#"P
"+ *
4+ 7
.+ )
5+ 6")
9+ M
:+ &(0" P
1
%
( "6
"/
!"6
26
*
,
1
$/
"7
$
!#
$/
-%
". 0
) !"
*#
!#
5!4
#
!
!
%(
!# → >
#
!
!"
,
1
!"
5!4
!
!# ?→
#
5!4
"
) '
*
,
!
"*
,
1
!
!# → !
!" → !
!
!#
A
'"
* "6
* "64$4' 2 1"6%&
* 4"
* 4 α"
'
2
'
* "6"
6%&1
* "%6
2
6%&1
6%1
α
#4 0
1
$
$
6'&
2
6%&1
6'&
1%&6
2
6'& 2 $ "
1"6%& 2
6'&
6'&
6'&
) '
"*
27
*
,
B
&+
1!6%2Q"
#+ $
'&6
"+
'% R 61!
6'&
'%
4+ ". 0
.+ 0
6'&
'&6
6'&
% (
5+
'% R 61!
6'&
C
6'&
9+ $
'&6
$''% R 61!
) '
$
"*
,
"
(
%&'
:
%
) '
"*
28
$
,
/
&+
#+ ,
%
,/
"+
4+ ,
%
$
) '
"*
) '
"*
,
/
%& '0
HOH2C
O
CHO
α"
%& '0
O
CHO
29
$
,
/
*
α"
#H
A
%&'
!
%& '0
α"
%& '0
$
) '
"*
) '
"*
,
,/
D
%
CHO
H
OH
HO
H
C
HO
H
H
OH
HO
H
H
OH
H
OH
H
OH
H
O
CH2OH
CH2OH
Glucosio
H
Ciclizzazione
OH
H
H
OH
H
O
HO
O
HO
H
HO
H
H
OH
HO
H
OH
OH
H
OH
H
forma Piranosidica
forma Piranosidica
30
$
,
,/
+
(
(
:
:
α"
α"
67,
$
,/
33
) '
"*
) '
"*
,
D
%
31
$
,
,
%
%&'
(
(
%&'
N
N
C6H5
N
C6H5
2 1$%' 2 %&'
N+
N
C6H5
C6H5
N
N
H
C6H5
N
C6H5
-
2 1$''% 2 %$
Cl
&(!(#"
"
) '
$
"*
,
+
R
R
CHOH
2 %&66%$5%#
CHO
+
CH
R
%&'
NNHC6H5
R
2 % &66%$5%#
CHOH
CH
+
2
CHOH
NNHC6H5
C
2 6%&$5%#
O
CH
R
2 6%!
NNHC6H5
R
" %&'
C
CH
O
NNHC6H5
2 %&66%$5%#
C
CH
NNHC6H5
NNHC6H5
) '
"*
32
$
,
$%!$''6
-
,
%&'
L
6%!L
) '
$
"*
,
,
$
R
R
C
'0
NNHC6H5
$
22
C
N
N
CH
NNHC6H5
HC
6"
C6H5
2 $5%#6%&
N
"
) '
"*
33
*
,
&GGE$
%&'
(
,
R
HC
NH3
COO
) '
*
-
,
1
α β
/
(
"*
"
/
6
O
COOH
C
C
O
H2N
C
O
trichetoidrindene
R
C
O
O
CH
C
O
aldimmina
N
CH
H2O
C
CH
C
R
RCHO
O
ammina
R
O
H
O
C
C
N
CH
C
OH
O
R
O
base di Schiff
O
C
CH
C
- H2 O
O
O
- CO2
NH
C
C
C
R
C
NH 2 CH
CH
C
COOH
O
COOH
O
NH 2
O
C
C O
C
O
O
O
C
C
CH
N
C
C
O
O
dichetoidrindiliden dicheto idrindene
) '
"*
34
*
,
-
(
!(#"
"
!(#"P
(
"
"
/
"
(
A
(
R
HC
<
R
NH2 +
Ar
N
C
COOH
R
HC
O
O
" %&'
NH
C
O
H
N
Ar
NH
O
CH
C
C
N
O
Ar
OH
) '
*
"*
,
#4
1
&(0"
R
R
" %)
HC
NH2 + F
NO2
COOH
HC
H
N
NO2
COOH
O 2N
O 2N
) '
"*
35