Montmorillonite K-10 catalyzed Mannich reaction: Synthesis of aminonaphthoquinone derivatives from Lawsone

Article abstract of DOI:10.1080/00397911.2018.1466334

An efficient one-pot protocol for the synthesis of 2-((substituted amino)(4-phenyl)methyl)-3-hydroxy-naphthalene-1,4-dione derivatives has been developed by the three-component reaction of 2-hydroxy-naphthalene-1,4-dione, aromatic aldehydes and anilines/heterocyclic amines using montmorillonite K-10 as a catalyst. The advantages of this method include short reaction time, excellent yield and easy work-up.

Full text of DOI:10.1080/00397911.2018.1466334

Synthetic Communications
An International Journal for Rapid Communication of Synthetic Organic
Chemistry
ISSN: 0039-7911 (Print) 1532-2432 (Online) Journal homepage: http://www.tandfonline.com/loi/lsyc20
Montmorillonite K-10 catalyzed Mannich reaction:
Synthesis of aminonaphthoquinone derivatives
from Lawsone
Sankaranarayanan Jayashree & Kalegowda Shivashankar
To cite this article: Sankaranarayanan Jayashree & Kalegowda Shivashankar (2018):
Montmorillonite K-10 catalyzed Mannich reaction: Synthesis of aminonaphthoquinone derivatives
from Lawsone, Synthetic Communications, DOI: 10.1080/00397911.2018.1466334
To link to this article: https://doi.org/10.1080/00397911.2018.1466334
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https://doi.org/10.1080/00397911.2018.1466334
Montmorillonite K-10 catalyzed Mannich reaction:
Synthesis of aminonaphthoquinone derivatives
from Lawsone
Sankaranarayanan Jayashree and Kalegowda Shivashankar
P.G. Department of Chemistry, Central College Campus, Bangalore University, Bangalore, Karnataka, India
ABSTRACT
ARTICLE HISTORY
Received 21 February 2018
An efficient one-pot protocol for the synthesis of 2-((substituted
amino)(4-phenyl)methyl)-3-hydroxy-naphthalene-1,4-dione derivatives
has been developed by the three-component reaction of 2-hydroxy-
naphthalene-1,4-dione, aromatic aldehydes and anilines/heterocyclic
amines using montmorillonite K-10 as a catalyst. The advantages of
this method include short reaction time, excellent yield and easy
work-up.
KEYWORDS
Lawsone; Mannich reaction;
montmorillonite K-10;
naphthoquinone; pigment
GRAPHICAL ABSTRACT
Introduction
Multicomponent reactions which combine three or more substrates in one pot have
gained considerable attention in recent times. These reactions have avoided the tedious
steps of protection and deprotection of functional groups, isolation of intermediates,
thereby reducing the generation of waste.[1–11]
Naphthoquinones constitute a main class of naturally occurring compounds and exhibit
wide variety of fluorescent, pharmacological and medicinal properties such as antidia-
betic,[12] anti-HIV,[13] anticancer,[14] trypsin inhibitor,[15] anti-inflammatory,[16] molluscici-
dal,[17] antiallergic,[18] anticoagulant,[19] antiacute pancreatitis,[20] antibacterial,[21]
antimalarial[22] and antifungal activities.[23] Recently, bis-aziridinyl dimeric naphthoquinone
CONTACT Kalegowda Shivashankar
shivashankark@gmail.com
P.G. Department of Chemistry, Central College
Campus, Bangalore University, Bangalore – 560 001, Karnataka, India.
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/lsyc.
Supplemental data for this article can be accessed on the publisher’s website.
ß 2018 Taylor & Francis

2
J. SANKARANARAYANAN AND K. SHIVASHANKAR
derivatives displayed potent antileukemic activities[24] and the coumarin-naphthoquinone
conjugates targeted the human topoisomerase II effectively.[25] The presence of secondary
amino group in naphthoquinones has led to interesting biologically active compounds such
as 2,2-dimethyl-3-phenylamino-2,3-dihydronaphtho[1,2-b]furan-4,5-diones which are active
against Chagas disease[26] and phenylaminonaphthoquinones with excellent cytotoxic activ-
ities.[27] Naphthoquinones also exhibited electrochemical properties,[28] nonlinear optical
properties,[29] potent organic fluorescent switching property[30] and orange/red light emit-
ting property in OLEDs.[31]
Lawsone (2-hydroxy-naphthalene-1,4-dione) is a natural dye (orange color) present in
henna plants. People have been using Lawsone as cosmetic dye for hair, finger nails,
silk, wool, leather, skin, etc., since the Bronze age[32] and for the detection of latent fin-
ger marks on paper surfaces.[33] A literature survey revealed that one pot synthesis of
these scaffolds have been achieved by employing catalysts such as InCl3,[34] p-toluene
sulfonic acid,[35] phenylphosphinic acid,[36] ionic liquids,[37] copper oxide[38] and den-
drimers.[39] But these methods involved the use of costly reagents, toxic solvents, long
reaction time and harsh conditions. Therefore, there is a need for efficient protocol to
obtain these valuable organic pigments.
In recent years, montmorillonite K-10 has gained extensive attention in organic
synthesis due to its unique properties of readily affordable, commercially available, non-
hazardous and tolerance to moisture as well as air making it the ideal catalyst. Owing to
these advantages, montmorillonite K-10 has been explored as an efficient catalyst for
various organic transformations such as Diels-Alder reaction,[40] Pinacol-Pinacolone
rearrangement,[41] Friedlander synthesis,[42] Fischer indole synthesis,[43] pyrolytic elimin-
ation reaction[44] Friedel-Crafts acylation and alkylation,[45] Heck vinylation,[46] and for-
mylation of phenols[47] without loss of its activity.
In connection with our consistent interest in the development of efficient synthetic
methodologies,[48–59] we report herein a new and efficient protocol using clay catalytic
system to access the synthesis of relevant scaffolds and some novel aminonaphthoqui-
none derivatives with benzothiazole moiety from readily available substrates.
Results and discussion
First, to find the standard conditions, the reaction of Lawsone (1), 4-nitrobenzaldehyde
(2e) and 4-nitroaniline (3c) in acetonitrile was selected as a model. When the reaction
was carried without any catalyst at ambient temperature and reflux, no desirable product
(4g) was obtained even after prolonged reaction time. This pointed out clearly that a
catalyst shall absolutely be needed for this reaction. When this three-component reaction
was attempted using L-proline (10 mol%) as a catalyst at ambient temperature, it was
observed that the reaction was end after 12 h yielding 45% of the product. We then
focused on Lewis acid catalysts and among these, zinc chloride, iodine, bismuth nitrate
pentahydrate and montmorillonite K-10 has resulted in 20%, 33%, 38% and 58% of
target product (4g), respectively.
We next performed a screening of various solvents such as water, chloroform, tolu-
ene, xylene, dichloromethane, tetrahydrofuran and ethanol. The results of Table 1
revealed that ethanol was the most suitable solvent for the reaction in terms of time,
temperature and yield. Subsequent experiments revealed that catalyst loading could be

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3
Table 1. Optimization studies for the synthesis of (4g).
NO2
O
H
O
NH2
NO2
Solvent, Temperature,
+
O
+
Time, Montmorillonite K-10,
Catalyst loading
OH
N
H
O
NO2
NO2
2e
OH
1
3c
O
4g
Entry
Solvent
Water
Chloroform
Toluene
Acetonitrile
Xylene
Dichloromethane
Temp (ꢀC)
Time (h)
Catalyst (mol%)
Yield (%)
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
Reflux
Reflux
Reflux
Reflux
Reflux
Reflux
Reflux
Reflux
60
40
RT
RT
RT
8
12
15
12
16
12
15
8
8
8
8
8
10
10
10
10
10
10
10
10
10
10
10
5
60
20
30
58
27
25
15
84
86
90
93
62
41
34
93
THF
Ethanol
Ethanol
Ethanol
Ethanol
Ethanol
Ethanol
Ethanol
Ethanol
8
8
8
3
2
15
RT
RT
Table 2. Synthesis of aminonaphthoquinone derivatives from Lawsone.
Time
(h)
S.No.
1
R1
Ar
Product
Yield (%)
H
4a
8
93
2
3
H
4b
4c
8
85
88
H3C
H3C
4-CH3
8.5
(continued)

4
J. SANKARANARAYANAN AND K. SHIVASHANKAR
Table 2. Continued.
Time
(h)
S.No.
4
R1
Ar
Product
Yield (%)
4-Cl
4d
10
83
H3C
5
6
7
8
4-Br
4e
4f
10
8
90
81
93
90
H3C
4-CH3
4-NO2
4-Cl
O2N
O2N
O2N
4g
4h
8
8.5
9
4-Cl
4i
9
85
83
90
81
83
91
H3CO
H3CO
10
11
12
13
14
4-NO2
4j
8.25
2-NO2
4k
4l
8
2,6-(CH3)2
3,4,5-(OCH3)3
4-NO2
8.25
10
8
4m
4n
N
(continued)

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5
Table 2. Continued.
Time
(h)
S.No.
15
R1
Ar
Product
Yield (%)
4-NO2
4o
8
93
H
N
N
S
16
H
4p
8.25
89
N
S
17
18
4-NO2
4-OH
4q
4r
8
8
92
90
N
S
N
S
19
20
4-Br
4s
4t
8.5
93
87
N
S
4-CH3
8
N
optimum at 10 mol% (Table 1, entry 11), but lower amounts were detrimental. It is
noteworthy that the ratio of the three starting substrates has important influence on the
yield of this reaction. When the ratio of 1/2e/3c was 1:1:1, the yield was raised to 93%.
Further altering the ratio, no progress of yield was observed.
In order to extend the above reaction to the library system, different substituted ben-
zaldehydes 2(a–i) and aromatic amines 3(a–g) were allowed to react with Lawsone to
give the aminonaphthoquinone derivatives 4(a–t) and representative examples are pre-
sented in Table 2. Benzaldehydes carrying both electron-donating and electron-
withdrawing substituents displayed high reactivity under this optimized conditions to
afford the desired products. Aromatic amines tethered with electron-donating and elec-
tron-withdrawing substituents showed similar reactivity and reacted efficiently to afford
the target products. Heterocyclic amines also exhibited a high reactivity under this
standard condition to yield the final products. The aminonaphthoquinones reported by
Dabiri et al.[34] (4a, 4b, 4c, 4e) and the compounds reported by Shahram et al.[39] (4d,
4f, 4g, 4h, 4i, 4j, 4h, 4n, 4o) are also obtained efficiently using this current protocol. It

6
J. SANKARANARAYANAN AND K. SHIVASHANKAR
Scheme 1. Plausible mechanism for the synthesis of aminonaphthoquinone derivatives.
is noteworthy that it is possible to synthesize a series of aminonaphthoquinones
containing phenyl, pyridyl, benzimidazolyl and benzothiazolyl moieties. To the best of
our knowledge, this is the first report for the synthesis of aminonaphthoquinone deriva-
tives with benzothiazolyl moiety.
A speculative mechanistic explanation for this reaction based on previously reported
literature[34,39] is provided in Scheme 1. In the first step, aromatic amines attacked the
activated benzaldehydes (A) to form activated imines (B). The latter compounds reacted
with Lawsone, to give an intermediate (C) that underwent tautomerization to yield the
products. Montmorillonite K-10 is likely to enhance the rate of Mannich reaction.
Conclusion
To concise, we reported a range of aminonapthoquinone derivatives with complete con-
trol over the substitution pattern. Mild reaction conditions, easy work-up and catalyst
recovery are prominent features of this protocol. Furthermore, a promising pathway for
the introduction of heterocyclic amines like 2-aminopyridine, 2-aminobenzimidazole
and 2-aminobenzothiazole is explored.
Experimental
General information
The melting points were recorded on an Electrothermal melting point apparatus. The
FT-IR (ATR) analysis was carried out on Cary 630 FT-IR spectrophotometer (Agilent
1
Technologies, Stevens Creek Blvd, Santa Clara, USA). H NMR (for 400 MHz) and 13C
NMR (for 100 MHz) spectra were recorded on a Bruker spectrometer using DMSO-d6

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SYNTHETIC COMMUNICATIONSV
7
as a solvent and Tetra Methyl Silane (TMS) as an internal standard. The chemical shifts
are expressed in d ppm. The mass analysis was recorded on a Micro Mass QTOF mass
spectrometer. The purity of the compounds was checked by Thin Layer
Chromatography (TLC).
Typical experimental procedure for the preparation of 2-hydroxy-3-
((4-nitrophenyl)(4-nitrophenyl)amino)methyl)naphthalene-1,4-dione (4g)
A mixture of 4-nitrobenzaldehyde (0.151 g, 1 mmol), 4-nitroaniline (0.138 g, 1 mmol),
2-hydroxy-naphthalene-1,4-dione (0.174 g, 1mmol) and montmorillonite K-10 (0.005 g,
10 mol %) was stirred in ethanol (3 mL). After the completion of the reaction, as indicated
by TLC, the mixture was diluted with CH2Cl2 and the catalyst was separated by filtration.
The catalyst was washed thoroughly with acetone and dried. The recovered catalyst was
reused up to four runs without any significant loss of its activity. The solvent was evapo-
rated under reduced pressure to get the crude product that was recrystallized from ethanol.
2-Hydroxy-3-((4-nitrophenyl)(4-nitrophenyl)amino)methyl)naphthalene-
1,4-dione (4g)
Yield 93%; a yellow solid; mp: 134–136 ꢀC. IR (ATR cmꢁ1): 3408 (OH), 3334 (NH),
1
1685 (C¼O), 1656 (C¼O); H NMR (400 MHz, DMSO-d6): d 11.23 (s, 1H, OH), 10.13
(s, 1H, NH), 8.15–6.79 (m, 12H, Ar-H), 6.08 (s, 1H, CH) ppm; 13C NMR (100 MHz,
DMSO-d6): d 183.1, 181.3, 153.4, 151.2, 149.2, 146.7, 136.2, 135.0 (2C), 131.4, 130.2,
128.4 (2C), 127.0 (2C), 126.7 (2C), 125.2 (2C), 117.1, 114.5 (2C), 52.3 ppm.
Acknowledgments
S.J. is thankful to CSIR for providing Senior Research Fellowship (SRF).
Funding
This study was supported by Council of Scientific and Industrial Research (CSIR), New Delhi,
India [Grants Reference no. 02(0172)/13/EMR-II, Dated: 21.10.2013].
Supporting information
This material can be found via "Supplementary Content" section of this article's webpage.
ORCID
Kalegowda Shivashankar
http://orcid.org/0000-0001-6419-341X
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