Ultrasound-Promoted One-Pot Three-Component Synthesis of β–Amino Carbonyl Compounds Using Manganese Perchlorate

Full text of DOI:10.1080/00304948.2020.1805995

Organic Preparations and Procedures International
The New Journal for Organic Synthesis
ISSN: (Print) (Online) Journal homepage: https://www.tandfonline.com/loi/uopp20
Ultrasound-Promoted One-Pot Three-Component
Synthesis of β–Amino Carbonyl Compounds Using
Manganese Perchlorate
Bhupinder Kaur & Harish Kumar
To cite this article: Bhupinder Kaur & Harish Kumar (2020) Ultrasound-Promoted One-Pot Three-
Component Synthesis of β–Amino Carbonyl Compounds Using Manganese Perchlorate, Organic
Preparations and Procedures International, 52:5, 474-477, DOI: 10.1080/00304948.2020.1805995
To link to this article: https://doi.org/10.1080/00304948.2020.1805995
Published online: 23 Sep 2020.
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ORGANIC PREPARATIONS AND PROCEDURES INTERNATIONAL
2020, VOL. 52, NO. 5, 474–477
https://doi.org/10.1080/00304948.2020.1805995
OPPI BRIEF
Ultrasound-Promoted One-Pot Three-Component Synthesis
of b–Amino Carbonyl Compounds Using Manganese
Perchlorate
Bhupinder Kaur and Harish Kumar
Department of Chemistry, Sant Longowal Institute of Engineering & Technology, Longowal, India
ARTICLE HISTORY Received 8 August 2019; Accepted 3 May 2020
The Mannich reaction is a key method for C-C bond formation leading to b-amino car-
bonyl compounds, which are important intermediates for diverse pharmaceuticals and
natural products.1,2 However, most methods rely on a two-component system using
pre-formed electrophiles, such as imines, and stable nucleophiles, such as enolates, enol
ethers or enamines.3–10 Compared to the direct three-component Mannich reaction,
these methods involve the preparation and isolation of intermediates, which is more
complicated and not atom economic.
Some methods reported for the direct Mannich reaction11–12 are catalyzed by organic
or mineral acids. Recently, some “one-pot” Mannich reactions have been performed in
the presence of lipase,13 guanidine hydrochloride,14 sulfamic acid,15 ionic liquid,16
perchloric acid,17 Fe(cp)2PF6,18 adenine,19 Cs2.5H0.5PW12O40,20 organoantimony com-
plexes,21 silica supported aluminum chloride,22 bismuth triflate,23 boric acid/glycerol,24
camphorsulfonic acid,25 polyaniline,26 silica sulfuric acid,27 NaBAr4F,28 GFQAS
(10%NaOH/10%TsOH),29
organobismuth(III)
perfluorooctanesulfonate30
and
(RE(OPf3)) in fluorous media.31 Several of these methods suffer from drawbacks such as
the corrosive nature of many of the catalysts, harsh reaction conditions, moderate
yields, complex work-up and purification procedures; furthermore, most of the one-pot
Mannich reactions are slow (4-44h). Therefore it was useful to develop a one-step
method to synthesize these compounds. Recently manganese perchlorate hexahydrate, a
dry, odorless, pink crystalline solid has emerged as an efficient and promising catalyst
for the synthesis of organic compounds.32–34 We now report the ultrasound assisted
one-pot approach to the Mannich reaction of aromatic aldehydes, amines and ketones
in ethanol catalyzed by manganese perchlorate hexahydrate at room temperature
(Scheme 1).
Initially, the model reaction of acetophenone (1), benzaldehyde (2a, R1 ¼ H) and
aniline (3a, R2 ¼ H) was chosen for the optimization of the catalyst. It was noted that,
under ultrasonic irradiation, 7 mol % of manganese perchlorate was optimum to carry
out the reaction. Ethanol was found to be a better solvent than water. See Table 1 for
our results; the table includes a comparison of reactions done with and without
CONTACT Bhupinder Kaur
hk67@rediffmail.com
Department of Chemistry, Sant Longowal Institute of
Engineering & Technology, Longowal (Pb.), India
ß 2020 Taylor & Francis Group, LLC

ORGANIC PREPARATIONS AND PROCEDURES INTERNATIONAL
475
Scheme 1. Three-component Mannich reactions.
Table 1. Manganese perchlorate catalyzed Mannich reaction at room temperature.
Without Ultrasonication
Under Ultrasonication
mp
lit. mpref
(0C)
Cmpd
R1
R2
Time (min)
Yield (%)
Time (min.)
Yield (%)
(0C)
4a
4b
4c
4d
4e
4f
4g
4h
4i
H
H
H
H
H
H
H
3-Br
H
3-Br
4-CH3
4-F
290
300
320
300
350
280
320
320
280
280
300
280
300
28
35
35
35
29
35
28
26
30
32
35
20
28
55
45
42
50
50
55
45
45
55
45
50
55
50
95
92
94
90
88
92
90
94
93
93
88
87
83
172-175
115-117
163-165
117-119
156-158
132-135
89-91
125-128
121-123
171-173
159-161
116-118
119-121
174-17615
113-11615
165-16835
116-11815
154-15615
134-13715
91-9215
4-Cl
4-HO
4-CH3
4-NO2
4-CH3O
4-NO2
3-HO
H
H
H
H
H
125-12715
122-12415
171-17215
162-16315
116-11715
118-12015
4j
4k
4l
2-Cl
2-NO2
4m
sonication. The model reaction, for example, gave 95% yield of 4a in 55 min with sonic-
ation, whereas the reaction done without sonication took 290 min and gave only
28% yield.
In conclusion, the present methodology has significant advantages over the reported
methods and includes the facts that (1) the reaction and the work-up procedure are
simple; (2) the products are isolated in good to excellent purity and yields; and (3) an
inexpensive catalyst is used.
Experimental section
All melting points were determined in open capillaries, and are uncorrected. IR spectra
were acquired as KBr pellets on a Perkin-Elmer spectrophotometer. NMR spectra were
acquired on an AL-300F (Bruker) FT NMR spectrophotometer using CDCl3 as internal
standard. Sonication was performed in an Elma Transonic T 310/H Ultrasonic cleaner
(with a frequency of 35 KHz), Hans Schmidbauer GmbH & Co., Germany. Safety
Notes: Do not store manganese perchlorate hexahydrate near or in contact with com-
bustible materials such as cotton, paper, rags, grease, oil, or organic compounds.
Manganese perchlorate must be stored in secondary containment with sufficient cap-
acity to hold the entire contents in case of breakage of the primary container.
Manganese(II) perchlorate hexahydrate is explosive under anhydrous conditions on
heating and should be treated with caution. On long exposure, it can cause irritation to

476
B. KAUR AND H. KUMAR
the eyes, skin and respiratory system. Gloves and face mask should be worn while pre-
paring and working with manganese perchlorate hexahydrate. Operations should be
done in a well-ventilated hood behind a safety shield. All workers must be thoroughly
trained before using this material. The reactions were performed in open vessels.
Typical procedure
To a mixture of benzaldehyde (1.06 g, 10.0 mmol), acetophenone (1.20 g, 10.0 mmol),
aniline (0.93 g, 10.0 mmol) and ethanol (20 ml), manganese perchlorate hexahydrate (See
Safety Notes above.) (0.25 g, 7 mole %) was added in a beaker and the mixture was soni-
cated at ambient temperature (cold water was added in sonicator after every 15 minutes
to maintain the ambient temperature) behind a safety shield in the hood for the time
indicated in Table 1. The completion of the reaction was monitored by TLC (silica gel,
petroleum ether and ethyl acetate in ratio 7:3). After the completion of the reaction, the
solid formed was collected and recrystallized from ethanol to afford the pure product.
All of the products were known compounds and were identified on the basis of com-
parison of their melting points with the appropriate literature values, as cited in
Table 1.
ORCID
Harish Kumar
http://orcid.org/0000-0002-5212-7789
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