Академический Документы
Профессиональный Документы
Культура Документы
N
O
2
N
+
O O
H
O
H
H
O
H
H
H
+
H
O O
H
O
H
H
H
H
O
H
H
O O
H H
O
H
H
+
FORMACIN DE LA ACROLENA
H
O
H
H
+
O O
H H
O O
H H
H
O
H
FORMACIN DE LA ACROLENA
1er. MECANISMO PROPUESTO. ADICIN-1,4
NO
2
N
H
H
H
O
+
O
H
N
O
2
N
H H
O
H
N
O
2
N
H
O
H
H
H
O
H
-
H ,
O
H
H
H
+
H
O
H
H
O
2
N
N
H
+
H
Tautomera ceto-enlica
O
H
O
2
N
N
H
H
N
O
2
N
O
H
H
H
+
O
H
O
2
N
N
H
O
H
H
H
O
H
H
Ciclizacin. Reaccin SEA
+
O
H
O
2
N
N
H
O
H
H
H
-
H ,
O
H
O
2
N
N
H
H
+
N
H
O
2
N
+
O
2
N
N
H
H
O
H
H
O
H
H
H
+
H
1,2-dihidro-6-nitroquinolina
Deshidratacin. Formacin de la 1,2-dihidroquinolina
2o. MECANISMO PROPUESTO. ADICIN-1,2
Formacin de la imina
NO
2
N
H
H
+
O
H
O
H
N
O
2
N
H H
O
H
Formacin de la imina
+
-
H ,
H
O
H
H
N
O
2
N
O
H
H H
O
H
H
N
O
2
N
H
O
H
H
N
O
2
N
H
O
H
H
+
H
Equilibro cido-base: sal de iminio-imina
Cicloadicin [2+2]
O
H
H
+
N
O
2
N
H
-
H ,
O
H
H
H +
N
O
2
N
+
H
N
O
2
N
H
N
N
H
O
2
N
NO
2
N
Sal de 1,3-diazetolio
N
N
H
O
2
N
NO
2
N
N
H
O
2
N
NO
2
Formacin del carbocatin
O
2
N
H
NO
2
N
N
O
2
N
NO
2
N
N
H
H
O
2
N
NO
2
N
N
H
H
O
H
+
H
O
H
H
Ciclizacin. Reaccin SEA. Formacin de
Benzo[e]-1,3-diazina
Benzo[e]-1,3-diazina
+
+
O
2
N
NO
2
N
N
H
H
H
O
H
H
O
H
H
-
H ,
O
2
N
NO
2
N
N
H
+
H
O
2
N
NO
2
N
N
H
H
O
2
N
NO
2
N
N
H
H
Formacin del carbocatin
O
2
N
N N
H H
O
2
N
N N
H H
N
O
2
N
H
+
O
2
N
N N
H H
NO
2
N
H
Formacin de la 1,2-dihidroquinolina
+
-
H
,
(25)
+
O
As
O
As
O
O O
H
O
H
H
(26)
O
As
O
As
O
O O
H
H
O
H
+
H
Reaccin de oxidacin. Formacin de la quinolina
N
O
2
N
H
(13)
+
(27)
N
O
2
N
H
O
As
H
O
O O
As
O
(26)
O
As
O
As
O
O O
H
+
H
O
H
H
N
O
2
N
O
As
H
O
O
H
As
O
O
-
H
,
N
O
2
N
As
O
H
O
As
O
H
O
O
H
O
H
H
H
O
H
+ +
+
H
O
H
H
N
O
2
N
As
O
H
O
+
N
O
2
N
As
O
H
O
As
O
H
O
O
O
As
O O
H
+
+
H
O
H
-
H
,
N
O
2
N
H
As
O O
As
O O
H
N
O
2
N
+
H
O
H
H
+
H
Reaccin redox
N
O
2
N
H
+
H
O
H
-
H
,
N
O
2
N
+
H
O
H
H
+
H
H
O
H
+
2
2
+
O C O
+
N
O
2
N
H
-
H
,
O Na
C
Na O
O
N
O
2
N
O
C
O
O
H H
O
C
O
O
H H
+
H
Reaccin cido-base
SNTESIS DE DOEBNERMILLER
Se nombra as por los investigadores alemanes Oscar Dbner
(Doebner) (1850-1907) y Wilhelm von Miller (1848-1899).
Doebner, O.; Miller, W. v. Ber., 1881, 14, 2812.
Doebner, O.; Miller, W. v. Ber., 1883, 16, 1664 & 2464.
Doebner, O.; Miller, W. v. Ber., 1884, 17, 1712.
2
2 4
2
FORMACIN DEL ACETALDEHDO Y DEL
CROTONALDEHDO
2 4
2 4
Combes, A. Bull. Chim. Soc. France 1888, 49, 89.
SNTESIS DE COMBES
SNTESIS DE COMBES
H
O
2
N
N
H H
H
O
2
N
N
H H
H
+
O
O
O
O
H
O
O
H
O
2
N
N
O
H
O H
H
H
AcO:
H OAc
O
2
N
N
O
H
O H
H
H
O
2
N
N
O
H
H
H O
H
+
O
2
N
N
O
H
H
H
O H
+
O
2
N
N
O
H
H
+
H O
H
H
+
H O S
O
O
O H
O
2
N
N
O
H
H
O
2
N
N
O
H
H
H
O
2
N
N
O
H
H
H
O
2
N
N
O
H
H
H
O
2
N
N
O
H
H
H
H
O
2
N
N
O
H
H
H
O
2
N
N
O
H
H
H
H O S
O
O
O H
+
+
O
2
N
N
O
H
H
H
H
O
2
N
N
H
H
O
H
H +
NaOH
O S
O
O
O H
O
2
N
N
H
+ O
H
H +
Na
2
SO
4
Ms que la SEA, se considera una ciclizacin electrocclica de un
1,3,5-3-azatrieno
Modificaciones:
REACCIN DE POVAROV
MECANISMO DE LA
REACCIN DE
POVAROV
Unprecedented regio and stereocontrol in Povarov reaction of
benzylidene-(3-nitrophenyl)amine Paul J . Stevenson and Isla
Graham, Arkivoc, AM-717D 2003.
SNTESIS DE FRIEDLANDER
CONDICIONES BSICAS
CONDICIONES CIDAS
MECANISMO DE LA REACCIN DE FRIEDLANDER
CONDICIONES BSICAS
1) CONDENSACIN DE KNOEVENAGEL
KOH
H
2
O, EtOH
2) CICLIZACIN Y AROMATIZACIN
SNTESIS DE FRIEDLANDER
Rapid and efficient synthesis of poly-substituted quinolines assisted by
p-toluene sulphonic acid under solvent-free conditions: comparative
study of microwave irradiation versus conventional heating
C.-S. J ia, Z. Zhang, S.-J . Tu, G.-W. Wang, Org. Biomol. Chem., 2006, 4, 104-110.
MECANISMO DE LA REACCIN DE FRIEDLANDER
CONDICIONES CIDAS
1)CONDENSACIN DE KNOEVENAGEL?
FORMACIN DE LA ENAMINA?
MECANISMO DE LA REACCIN DE FRIEDLANDER
CONDICIONES CIDAS
1)CONDENSACIN DE KNOEVENAGEL?
FORMACIN DE LA ENAMINA?
O
NH
2
+
S
O
O
OH H
3
C
N
H
H
O
H
N
H
N
H
R
O
R
O
R
O
R
O
N
H
R
HO
N
R
Molecular iodine: a highly efficient catalyst in the synthesis of quinolines
via Friedlnder annulation
J . Wu, H.-G. Xia, K. Gao, Org. Biomol. Chem., 2006, 4, 126-129.
Ionic Liquid-Promoted Regiospecific Friedlander Annulation: Novel
Synthesis of Quinolines and Fused Polycyclic Quinolines
S. S. Palimkar, S. A. Siddiqui, T. Daniel, R. J . Lahoti, K. V. Srinivasan,
J. Org. Chem., 2003, 68, 9371-9378.
Indium(III) Trifluoromethanesulfonate: An Efficient Reusable Catalyst for
the Alkynylation-Cyclization of 2-Aminoaryl Ketones and Synthesis of 2,4-
Disubstituted Quinolines
K. C. Lekhok, D. Prajapati, R. C. Boruah, Synlett, 2008, 655-658.
Nickel-Catalyzed Cyclization of 2-Iodoanilines with Aroylalkynes: An
Efficient Route for Quinoline Derivatives
R. P. Korivi, C.-H. Cheng, J. Org. Chem., 2006, 71, 7079-7082.
SNTESIS DE PFITZINGER
ISATINA
SNTESIS DE
ISOQUINOLINAS
Deshidratacin . Formacin sales de nitrilio
Sntesis de Bischler-Napieralski
Reaccin SEA
Reaccin de Eliminacin
Reaccin con cloruro de oxalilo
A Versatile Cyclodehydration Reaction for the Synthesis of Isoquinoline
and -Carboline Derivatives
M. Movassaghi, M. D. Hill, Org. Lett., 2008, 10, 3485-3488.
The first Bischler-Napieralski cyclization in a room temperature ionic
liquid
Z. M. A. J udeh, C. B. Ching, J . Bu, A. McCluskey, Tetrahedron Lett., 2002, 43, 5089-
5091.
OTROS MTODOS
REACCIONES
PROPIEDADES
QUMICAS