Grinding and Milling: Two Efficient Methodologies in the Solvent-Free Phosphomolybdic Acid-Catalyzed and Mechanochemical Synthesis of <i>cis</i>-4-Amido-<i>N</i>-yl-2-methyl-tetrahydroquinolines

Kouznetsov, Vladimir V.; Merchán-Arenas, Diego R.; Martínez-Bonilla, Carlos A.; Macías, Mario A.; Roussel, Pascal; Gauthier, Gilles H.

doi:10.5935/0103-5053.20160117

Vladimir V. Kouznetsov ^**e-mail: kouznet@uis.edu.co, vkuznechnik@gmail.com

Laboratorio de Química Orgánica y Biomolecular, Universidad Industrial de Santander, Parque Tecnológico Guatiguara, Km 2 vía refugio, A.A. 681011 Piedecuesta, Colombia

Diego R. Merchán-Arenas

Grupo de Investigación e Innovación en Básicas, Universidad Manuela Beltrán, Calle de los Estudiantes 10-20 Ciudadela Real de Minas, A.A. 678 Bucaramanga, Colombia

Carlos A. Martínez-Bonilla

Laboratorio de Química Orgánica y Biomolecular, Universidad Industrial de Santander, Parque Tecnológico Guatiguara, Km 2 vía refugio, A.A. 681011 Piedecuesta, Colombia

Mario A. Macías

Grupo INTERFASE, Universidad Industrial de Santander, Carrera 27, Calle 9, Ciudad Universitaria, Bucaramanga, Colombia

Pascal Roussel

Université Lille Nord de France, Unité de Catalyse et de Chimie du Solide, Equipe Chimie du Solide, Avenue Dimitri Mendeleïev, Bâtiment C7, ENSCL/UST Lille 1, BP 90108, 59652 Villeneuve d'Ascq Cedex, France

Gilles H. Gauthier

Grupo INTERFASE, Universidad Industrial de Santander, Carrera 27, Calle 9, Ciudad Universitaria, Bucaramanga, Colombia

*e-mail: kouznet@uis.edu.co, vkuznechnik@gmail.com


entry	Solvent	Catalyst^a a mol% per mol of substrate; / mol%	Temperature / ºC	time / h	Yield^c c GC-MS monitored. rt: room temperature. / %
1¹⁹19 Kouznetsov, V. V.; Merchan Arenas, D. R.; Ortiz Areniz, C.; Meléndez Gómez, C.; Synthesis 2011, 24, 4011; Merchan Arenas, D. R.; Rojas Ruíz, F. A.; Kouznetsov, V. V.; Tetrahedron Lett. 2011, 52, 1388; Kouznetsov, V. V; Gómez Melendez, C. M.; Parada Luna, L. K.; Bermudez, J. H.; Méndez Vargas, L. Y.; Acevedo Muñoz, A.; Mol. Divers. 2011, 15, 1007.	MeOH	PA (50)	50	8	52
2¹⁹19 Kouznetsov, V. V.; Merchan Arenas, D. R.; Ortiz Areniz, C.; Meléndez Gómez, C.; Synthesis 2011, 24, 4011; Merchan Arenas, D. R.; Rojas Ruíz, F. A.; Kouznetsov, V. V.; Tetrahedron Lett. 2011, 52, 1388; Kouznetsov, V. V; Gómez Melendez, C. M.; Parada Luna, L. K.; Bermudez, J. H.; Méndez Vargas, L. Y.; Acevedo Muñoz, A.; Mol. Divers. 2011, 15, 1007.	MeOH	PA (100)	50	8	62
3	MeCN	-	rt	3	nil
4²⁴24 Merchán Arenas, D. R.; Martínez Bonilla, C. A.; Kouznetsov, V. V.; Org. Biomol. Chem. 2013, 11, 3655.	MeCN	PMA (5)	rt	4	60
5	MeCN	PMA (5)	50	4	74
6²⁴24 Merchán Arenas, D. R.; Martínez Bonilla, C. A.; Kouznetsov, V. V.; Org. Biomol. Chem. 2013, 11, 3655.	MeCN	PMA (10)	rt	0.5	92
7	MeOH	PMA (10)	rt	1	85
824	MeCN	PMA/SiO₂^b b catalyst (PMA/SiO2) loading 50% m/m based on aniline’s (1) weight (wt.%);	50	2	50
924	MeCN	PMA/SiO2 (recycled)^b b catalyst (PMA/SiO2) loading 50% m/m based on aniline’s (1) weight (wt.%);	50	2	30
10	PEG-400	PMA (5)	rt	2	nil
11	PEG-400	PMA (5)	60	3	35

entry	Material	Catalyst / (mol%)^a a mol% per mol of substrate;	Solvent	time / h	Yield^b b GC-MS monitored; / %
1	agate	10	-	0.25	18
2	agate	10	-	0.5	25
3	agate	10	-	0.75	27
4	agate	10	-	1	32
5	agate	10	-	2	55
6	agate	10	-	3	65
7	agate	10	-	4	65
8	steel	10	-	3	40
9	agate	10	H₂O, 10% m/m^c c catalyst (PMA/SiO2) loading 50% m/m based on aniline’s ( 1 ) weight (mass fraction wt.%);	3	10
10	agate	10	PEG-600, 10% m/m^c c catalyst (PMA/SiO2) loading 50% m/m based on aniline’s ( 1 ) weight (mass fraction wt.%);	3	45
11	agate	10	SDS, 10% m/m^c c catalyst (PMA/SiO2) loading 50% m/m based on aniline’s ( 1 ) weight (mass fraction wt.%); ,^d d aqueous solution 12 mmol L-1, pH = 1.	3	53
12	agate	PMA/SiO₂, 10% m/m^c c catalyst (PMA/SiO2) loading 50% m/m based on aniline’s ( 1 ) weight (mass fraction wt.%);	-	3	55


entry	R¹	R²	R³	Yield^a a GC-MS monitored. / %
1	COMe	H	Me	63
2	OMe	H	Me	61
3	H	H	Me	89
4	OMe	H	H	60
5	COMe	-(CH₂)₂-		74
6	H	-(CH₂)₂-		55


entry	Compound	R¹	R²	R³	Yield / %
1	3a	COMe	H	Me	65
2	3b	H	H	Me	56
3	3c	OMe	H	Me	64
4	3d	COMe	H	H	76
5	3e	H	H	H	63
6	3f	OMe	H	H	60
7	3g	COMe	-(CH₂)₂-		69
8	3h	H	-(CH₂)₂-		67
9	3i	OMe	-(CH₂)₂-		72

[1] *e-mail: kouznet@uis.edu.co, vkuznechnik@gmail.com

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Grinding and Milling: Two Efficient Methodologies in the Solvent-Free Phosphomolybdic Acid-Catalyzed and Mechanochemical Synthesis of cis-4-Amido-N-yl-2-methyl-tetrahydroquinolines