UNIVERSIDAD AUTÓNOMA DEL ESTADO DE MORELOS

Facultad de Ciencias Químicas e Ingeniería

P.E. Químico Industrial

Química Verde

Microwave-assisted solvent-free and

catalyst-free Kabachnik–Fields reactions
for α-amino phosphonates

BAHENA GARCÍA MAURICIO

ESTRADA HERRERA DIANA ALONDRA
 THE FUNCTION OF A SOLVENT

Changing of solvent of a reaction can influence the

rate of that reaction, and it can be powerful
enough to change the reaction course itself.
A solvent could be deeply and inseparably
associated with the process of an organic
reaction through the solvation of the
reactants, products, transition-state or other
intervening species.
Nagendrappa, G. (2002). Organic Synthesis under Solvent-free Condition. An Environmentally Benign Procedure.
Resonance, 7(1), 64-77. 1
 Historically significant organic synthesis achieved by
Wöhler in 1828 belongs to the class of solid state
reaction
¿Products are different?

There are two experimental conditions employed to carry out the chemical reactions under
solvent-free conditions such as
(a) reaction on solid support
(b) reaction without any solvent, solid support, or catalyst

K. Tanaka, F. Toda. (2000) Solvent-free organic synthesis. Chem. Rev. 100(3), 1025–1074.
2
 ADVANTAGES OF SOLVENT-FREE REACTIONS
There is no reaction medium to collect, purify, and recycle, thus
eco-friendly.
Product purity is high, so avoids extensive purification using
chromatography, only recrystallization is required in some cases. Limitations
Reactions are facile, regioselective. Homogenous reactants should mix
High yield and less time for the completion of reaction. to a reaction system.
Green Approaches in Medicinal Chemistry for Sustainable Drug Solvents are required during workup
Design (e.g., extraction).
Process is cost effective. Unsuitable for solvent-assisted
Simple workup procedure and no need for specialized equipments. chemical reactions.
Functional group protection-deprotection can be avoided. High viscosity in reaction system.
Low energy consumption.
Solvent-free reactions are economic because organic solvents are
expensive.
Solvent-free reactions are less or no hazardous but in case of
reactions under solvents, solvents are volatile, flammable, toxic, and
carcinogenic.
More efficient with more selectivity as compared to reactions
carried out in solvents.
Mohan, B. y Krishna, B. (2020). Solvent-less reactions: Green and suinable approaches in medicinal chemistry. Advances
in Green Chemistry. pp 523-548. 3
 MULTICOMPONENT REACTIONS
These reactions are often discovered by serendipity, but rational design strategies are now playing
an increasing role because of their convergent nature, superior atom economy, and
straightforward experimental procedures in the construction of target compounds by the
introduction of several diversity elements in a single operation, resulting in substantial
minimizations of waste, labor, time, and cost. Further, chemo-and stereoselectivities.

Number of publications dealing with MCRs

under solvent-free conditions in the period
2000-2010

Shankar, M. y Sushobhan Chowdhury. (2012). Recent developments in solvent-free multicomponent reactions: a

perfect synergy for eco-compatible organic syntheisis. RSC Advances, 2, 4547–4592. 4
 In order to break down the complex notion of molecular diversity, we can distinguish three
fundamental levels of diversity:
(a) appendage diversity (combinatorial chemistry)
(b) stereochemical diversity
(c) scaffold diversity.

Different multicomponent reactions.

Shankar, M. y Sushobhan Chowdhury. (2012). Recent developments in solvent-free multicomponent reactions: a

perfect synergy for eco-compatible organic syntheisis. RSC Advances, 2, 4547–4592. 5
 By using these technologies, the solvent-less reactions become efficient and economic by
increasing the rate of reaction with reduced reaction time and high product yield.

 Microwave (MW) technology

 Ultrasonication
 Photocatalysis
 Grinding technique
 Milling technique

Process of reaction by ultrasonication

Mohan, B. y Krishna, B. (2020). Solvent-less reactions: Green and suinable approaches in medicinal chemistry. Advances
in Green Chemistry. pp 523-548. 6
 Photocatalysis (ultraviolet, visible, and IR irradiation)

Chemical reactions by grinding technique

Reactions precess involved in ball milling

B. Konig. (2017). Photocatalysis in organic synthesis—past, present, and future. Eur. J. Org. Chem. 1979–1981. 7
 The representation of Microwave-assisted organic synthesis (MAO S)
multidimensional advantages (a) Temperature profile of reaction mixture after t min as alerted
of microwave chemistry in by the treatment in traditional oil bath and microwaves; (b)
nanoscience and representation of oscillating field in conduction and dipolar
nanotechnology mechanisms; (c) activation energy diagram for the chemical
reaction under microwave conditions.

Kumar, A., Kuang, Y., Liang, Z. y Sun, X. (2020). Microwave chemestry, recent advancements, and eco-friendly microwave-
assisted synthesis of nanoarchitectures and their applications: a reviw. Materials Today Nano, 11. 100076. 8
 Microwave effects on organic reactions

Loupy, A. (2004). Solvent-free microwave organic synthesis as an efficient procedure for green chemistry. C. R. Chimie
7, 103-112. 9
 α-AMINO PHOSPHONATES

A catalyst-free Kabachnik–Fields
reaction of benzaldehyde, aniline, and
dimethyl phosphite was first attempted
using ethanol as a solvent.

Cherkasov, R. y Galkin, V. (1998). The Kabacnik-Fields reaction: synthetic potential and the problem of the mechanism.
Russian Chemical Reviews. 67(10), 857-882. 10
 RESULTS

• Primero:
Se llevó acabo reacción de
Kabachnik – Fields libre de
catalizador con diferentes
disolventes.
• Después:
Se exploraron reacciones de
Kabachnik- Fields en condiciones
libre de catalizador y libre de
disolventes.

Xue-Jun, M., Mao-Yi, L., Jian-Ping, Z. y Wei, Z. (2006). Microwave-assisted solvent-free and catalyst-free Kabachik-Fields
reactions for α-amino phosphonates. Tetrahedron Letters, 47. 1125-1127. 11
 • Para evaluar el alcance sintético,
se realizaron reacciones con
diferentes aldehídos y aminas con
dimetilfosfito:

• En resumen, se desarrolló una

síntesis asistida por microondas
Kabachnik–Fields sin catalizadores y
sin disolventes para la síntesis de a-
amino fosfonatos

Xue-Jun, M., Mao-Yi, L., Jian-Ping, Z. y Wei, Z. (2006). Microwave-assisted solvent-free and catalyst-free Kabachik-Fields
reactions for α-amino phosphonates. Tetrahedron Letters, 47. 1125-1127. 12
 Gracias por su
atención

EQUIPO LINZAGA