Azoxi-derivati

Preparare:
- reducerea nitrobenzenului in mediu alcalin;
- oxidarea azo- si hidrazobenzenului.
Proprietati:
N=N
reducere
N=N N=N
O
reducere
N=N
C
6
H
5
N=N C
6
H
5
O
N=N
OH
azoxibenzen
Azo-derivati
Preparare:
-reducerea azoxiderivatilor
-oxidarea hidrazoderivatilor
-reactia nitrozobenzenului cu amine aromatice primare
Proprietati:
-reactia de reducere
-reactia de oxidare
-formarea de saruri
C
6
H
5
N N=
(+)
Cl
-
H
..
C
6
H
5
N
N C
6
H
5
N C
6
H
5
N C
6
H
5
trans cis
NH NH
H
2
N NH
2
C
6
H
5
N=N C
6
H
5
C
6
H
5
NH NH C
6
H
5
+ C
6
H
5
NH
2
C
6
H
5
NH NH C
6
H
5
H
2
N C
6
H
5
HIDRAZODERIVATI
NH NH
H
2
N OCH
3
NH OCH
3 NH NH
H
2
N OCH
3
NH OCH
3
NH
2 NH NH
OCH
3
OCH
3
OCH
3
H
2
N
OCH
3
NH NH
OC
2
H
5
OC
2
H
5
H
2
N
NH
2
OC
2
H
5
OC
2
H
5
FENILHIDRAZINA
sarea de sodiu a acidului
C
6
H
5
NH NH SO
3
Na
SO
2
H
2 +
C
6
H
5
N=N SO
3
Na
C
6
H
5
N=N SO
3
Na NaCl +
C
6
H
5
N=N SO
3
Na Na
2
SO
3
+
+
C
6
H
5
N=N Cl
-
+
C
6
H
5
N=N Cl
-
HCl
+
HONO
+
C
6
H
5
NH
2
Preparare (metoda Fischer, 1878)
fenil-hidrazina
NaHSO
4
+
C
6
H
5
NH NH
2
HCl
HOH
+
C
6
H
5
NH NH SO
3
Na
sarea de sodiu a acidului
fenil-hidrazin-sulfonic
C=O
R
R
(H)
+
H
2
N NH C
6
H
5
C=N NH C
6
H
5
R
R
(H)
+
H
2
O
reactiv pt. gruparea carbonilica
C
6
H
5
N=N Cl
-
+
HONO
+
2 H
2
O C
6
H
5
NH
2
HCl
+
Diazoderivati aromatici
+
+
H
2
O
O=N OH H
+
repede
O=N OH
2
+
-
N=O
:
..
..
.. ..
:
..
nitrozamina
C
6
H
5
NH N=O
C
6
H
5
NH
2
N=O
SE
incet
C
6
H
5
NH
2
N=O
-
H
+
+
+
+
ion de diazoniu
nitrozamina
+
C
6
H
5
N=N
-
+
C
6
H
5
N=N OH
2
H
+
-
H
+
+
C
6
H
5
N=N OH
H
H
2
O
C
6
H
5
N=N Cl
-
+
+
HOH C
6
H
5
OH
+N
2
+
HCl
C
6
H
5
N=N Cl
-
+
+
N
2
+
HCl
CH
3
CH
2
OH CH
3
CHO 2 H
+
2
H C
6
H
6
+
nitrare
NO
2
acilare
NO
2
reducere
NO
2
Reactii ce au loc cu eliminarea grupei diazo
nitrare
NH CO CH
3
acilare
NH
2
reducere
NO
2
p-dinitrobenzen
HCl
+
N
2
+
H
NO
2
NO
2
H 2 alcool
N=N Cl
-
+
NO
2
NO
2
diazotare
NO
2
NH
2
NO
2
NO
2
NO
2
NH CO CH
3
NO
2
C
6
H
5
N=N Cl
-
+
N
2
+ + + KI C
6
H
5
I KCl
C
6
H
5
N=N Cl
-
+
HCl
+
H
+
BF
4
-
C
6
H
5
N=N BF
-
4
+
C
6
H
5
F +BF
3
+
+
+
C
6
H
5
N=N HSO
4
-
(
CuBr
)
CuCl
C
6
H
5
Cl
Br
( )
CuHSO
4
-
+
C
6
H
5
N=N Cl
-
+
+
+
CuCl CuCN C
6
H
5
CN N
2
+
benzonitril
C
6
H
5
N=N Cl
-
+
+
+ HCl N
2
+
H
2
S C
6
H
5
SH
C
6
H
5
NO
2
KNO
2
KCl N
2
+ +
+
+
C
6
H
5
N=N Cl
-
Ar N=N X
- incet
Ar
+
+ N=N + X
-
Ar
+
+ HOH
repede
Ar OH
+
H
+
X
-
+
H
+
HX
:
+
:
Mecanism:
(extragere de hidrogen)
.
.
.
CH
3
CHO
+
HX
+
ArH CH
3
CH
2
OH + X + Ar
X
+ N
2
.
Ar
Ar N=N X
+
+
H OH N=N OH
+
HCl
+
Cl
-
HCl
+ C
6
H
5
N=N H
2
N C
6
H
5
-
(CH
3
COONa)
C
6
H
5
N=N NH C
6
H
5
diazoaminobenzen
Reactii ce au loc cu pastrarea grupei diazo (r. de cuplare)
N=N
+
Cl
-
+ H N(CH
3
)
2
N=N N(CH
3
)
2
+
HCl
p-hidroxiazobenzen
p-dimetilaminoazobenzen
Ar N=N:
+
Ar N=N
..
..
+
+ ..
(-)
H NH
2
+
Ar N=N NH
2
+
H
-
H
+
Ar N=N NH
2
p-amino-azo-benzen
Mecanismul reactiilor de cuplare
mediu acid
Ar N=N +
+
OH
-
Ar N=N OH Ar N=N O
-
+ H
+
+
+ +
Ar N=N
C
6
H
5
O
-
Ar N=N C
6
H
4
O
-
H
+
mediu bazic
+
-
H
2
O
CH
3
N
H
COOC
2
H
5
HONO CH
3
N
NO
COOC
2
H
5
HOH
-
C
2
H
5
OH
-
CO
2
metil uretan nitrozometil uretan
CH
3
NH NO
KOH
CH
3
N= N OK
-
KOH
CH
2
=N=N
DIAZODERIVATI ALIFATICI
HX
diazoacetat de etil
(ester diazo-acetic)
esterul acidului
amino-acetic
- +
N=N
HX
+
N N X
-
CH
2
COOC
2
H
5
H
2
O
2
O=N OH
NH
2
CH
2
COOC
2
H
5
-
-
+
CH COOC
2
H
5
DIAZOMETAN
+
R OH CH
2
N
2
R OCH
3
+
N
2
R COOH
+
CH
2
N
2
R COOCH
3
+
N
2
R OH
n
CH
2
=N=N
n
N
2
+
(CH
2
)n
2ROOC CH=N=N
N
HC
N
N
CH COOR
N
ROOC
saponificare
decarboxilare
-2 H
N
N
N
N
1
2
3
4
5
6
ROOC
HC=CH
+
CH
2
=N=N
HC CH
H
2
C N
N
HC CH
HC NH
N
pirazol
R CH
2
COOR' HOR' + R CH=C=O
-
R COCl+CH
2
N
2
HCl
R CO CHN
2
N
2
+ R CO CH
..
FUNCTII MIXTE CU OXIGEN
Halogen Halogen--alcooli alcooli
structural: -OH si X legate de o catena hidrocarbonat alifatica
Preparare:
reactia alchenelor cu halogeni, in prezenta apei in exces;
tratarea la cald a polialcoolilor cu HCl/HBr/HI; tratarea la cald a polialcoolilor cu HCl/HBr/HI;
alcool alilic si HOCl;
oxid de etena si HCl.
Proprietati
- cele 2 grupe functionale au reactivitate chimica normala:
reactia cu KCN, eliminarea de hidracid in mediu bazic.
HALOGEN-FENOLI
structural:-OH si X grefate pe un nucleu aromatic
Preparare:
clorurarea si bromurarea fenolului;
din brom-amine prin diazotare si hidroliza.
Proprietati:
-acizi mai tari decat fenolii simpli; -acizi mai tari decat fenolii simpli;
-reactia cu carbonatul de sodiu (diferentiere de fenoli);
-reactia cu NaOH;
Reprezentanti
Cl
OH
CH
2
C
6
H
5
I
OH
Cl
CH
2
OH
Cl
II
CH
2
OH OH
Cl
Cl
Cl Cl
Cl
Cl
III
clorofen diclorofen hexaclorofen