AZINEAZINE
NN
N
N
N
N
Piridazina Pirimidina Pirazina
Piridazina (1,2-diazina)
ObtinereObtinere
POCl3
N
N
Cl
Cl
H2
Pd / C N
N
Piridazina
O
O
O
NH2
NH2- H2O
NH
NH
O
O
N
N
OH
OH
+
Piridazindiol
O
O
O
NH2
NH2 - H2O NH
NH
O
O
N
N
OH
OH
+
NH
NH
O
O
N
N
OH
OH
N
N
O
O
N
N
O
O+
Sint.Dien
[O]
1,4-Ftalazindiona
ftalhidrazida
[O] = hipoclorit de tert-butil, tetraacetat de Pb
Pirimidina (1,3-diazina)
O CNH2
NH2
ROOC
CH2
ROOC
EtO
- 2 ROH
HN
NHO
O
O
N
N OHHO
OH
Acid barbituricUree
+
Ester malonic
taut.
ObtinereObtinere
N
N OHHO
OH
POCl3 N
N ClCl
Cl
Zn, H2O N
NPirimidina
Derivaţi ai pirimidinei
Uracil (2,4-dihidroxi-pirimidina)
ROOC
CH2
OHC
EtOO C
NH2
NH2
N
NHO
OH
+ ROH + H2O
Uracil
+
Uree Ester formilacetic
Citosina (2-hidroxi-4-amino-pirimidina)
POCl3 N
NC2H5S
Cl
NH3 N
NC2H5S
NH2
H2O
HCl
N
N
NH2
HO
ROOC
CH2
OHC
EtO
N
NC2H5S
OH-ROH
+
Etil-tiouree Ester formilacetic
CNH
NH2
C2H5S-H2O
Citosina
2-Amino-pirimidina
ROOCCH2
OHC
EtO N
NH2N
OH
-ROH- H2O
CNH
NH2
H2N + POCl3 N
NH2N
Cl
N
NH2N
red.
2-Amino-pirimidina
N
N N
N N
N
N
N N
N
Reactivitate
Caracter aromatic – derivaţii substituiţi la nucleu cu grupe aril, halogen, alchil şi nitro - scade pe măsură ce se introduc la nucleu grupe –OH şi -NH2
- substituţia electrofilă decurge greu
ROOCC
ROOC
Et
Et
EtOC
NH2
ONH2
NH
NHO
O
O
Et
Et+ 2 ROH+
Veronal
Pirazina (1,4-diazina)
N
N
N
N
.... N
N
N
N
N
N
.. .. ..
.. ..N
N
..
....
R C=O
CHRNH2
CH R
O=C
H2N
R N
N
R
R R
R N
N
R
R R
R
+
2,3,5,6-tetra-alchilpirazine
ObtinereObtinere
N
N
N
N
N
N
N
N
N
N
NH
COCH3
COCH3
COCH3 N COCH3
2,5-dimetilpirazina 2,3,5,6-tetrametilpirazina 2-metil-3-etilpirazina 2-acetilpirazina
2-acetil-3-etilpirazina 2-acetil-1,4,5,6-tetrahidropiridina 2-acetilpirol
nuci prăjite nuci prăjite cafea prăjită
popcorn
cartofi copti
PUPURINERINE
N
N N
N
H
1
2
34
56 7
8
9
Obţinere
Sinteza Baeyer-Fischer
HN
NH
O
OO
HNO2 HN
NH
O
OO
NO4[H] HN
NH
O
OO
NH2HNCO HN
NH
O
OO
NHCO
NH2
-H2O N
N
N
NOH
HHO
OH
Acid uric
Acid barbituric Uramil
POCl3 N
N
N
NCl
HCl
Cl
red. N
N
N
N
HPurina
Sinteza Traube
ROOCC
NC
H
H
EtOC
NH2
ONH2
N
NHO
OH
NH2NH
NHO
NH
O
H
H- ROH
6-Aminouracil
+
Uree Ester cianacetic
HNO2 N
NHO
OH
NH2
NO
red. N
NHO
OH
NH2
NH2
5,6-Diaminouracil
- ROHN
NHO
OH
NH2
NHCOOR
Cl-COOR
Acid uric
N
N
N
NOH
HHO
OH
ROOCC
NC
H
H
EtOC
NH2
SNH2
N
NHS
OH
NH2
NH
NHS
NH
O
H
H-ROH
6-Aminotiouracil
+
Tiouree
HNO2
N
NHS
OH
NH2
NO
red. N
NHS
OH
NH2
NH2
Hipoxantina
N
N
N
NH
OH
HNO3HCOOH N
N
N
NH
HS
OH
ROOCC
NC
H
H
EtOC
NH2
HNNH2
N
NH2N
OH
NH2NH
NH
NH
O
H
HHN
-ROH
N
N
N
N
HH2N
OH
1. HNO2
2. red.N
NH2N
OH
NH2
NH2 HCOOH
Guanina
Guanidina
NCC
NC
HH
EtOCNH2
SNH2 N
NHS
NH2
NH2NH
NHS
NH
NH
H
H
1. HNO2
2. red.N
NHS
NH2
NH2
NH2 HCOOH N
N
N
N
HHS
NH2
HNO3 N
N
N
N
H
NH2
Tiouree Dinitrilmalonic
Adenina
N
N
N
N
HHO
OH
OHN
N
N
N
H
Cl
Cl
ClPOCl3 3HI N
N
N
N
H
EtO-Na+
KOH
NH3
N
N
N
N
H
OEt
EtO
Cl
N
N
N
N
H
OH
HO
HI
N
N
N
N
H
OH
Cl
Cl
HI
N
N
N
N
H
OH
1. NH3
2. HI
N
N
N
N
H
OH
H2N
N
N
N
N
HCl
NH2
Cl
HI
N
N
N
N
H
NH2
Adenina Guanina Hipoxantina Xantina
N
NN
N
NH2
OHOHATP
OP
OH
O
O P
O
OH
O P
O
OH
O CH2HO
N
CONH2
O
OHHO
OHOH
CH2 O P
OH
O
O P
O
O
O CH2O
Codehidraza I (DNP)
N
N
N
N
NH2
teobrominacafeina
teofilina
