3846
V. K. Tandon, H. K. Maurya / Tetrahedron Letters 51 (2010) 3843–3847
R3
R4
O
R2
R1
In situ
O
Step 2
Step 1
O
X
Cl
Cl
i) 1 eq 2, Et3N
ii) 0.5% LD or SDS, H2O
H2O, 0.5% LD
R5
O
R5
R6
O
º
or SDS; 6h, 50 C
HX
R6
R8
1a
R7
R7
R8 (1 eq)
7
8
Scheme 2. In situ one-pot synthesis of 8a–f: Reaction of 2,3-dichloro-1,4-naphthoquinone (1a) with 2 and 7, respectively (in situ), as shown in Table 6.
Table 6
Reagent and reaction conditions of reaction between 2,3-dichloro-1,4-naphthoquinone (1a) with phenols (2) and 7 as shown in Scheme 2
7, 8a
Step 1b (2)
Step 2 (7)
R7
Yields (%) of 8 in
X
R5
R6
R8
Tb (°C)
tb
LD
SDS
a
b
c
d
e
f
2b
2b
2b
2d
2e
2b
S
S
NH
NH
NH
O
H
H
H
H
H
OH
H
H
H
H
H
H
H
Me
H
Cl
Cl
H
H
H
H
H
H
Me
rt
rt
90
90
50
60
30 min
30 min
8 h
8 h
1 h
90
95
75
78
81
51
91
94
73
78
80
50
2 h
a
All compounds directly filtered as single product as monitored by TLC except 8f.
Optimized time and temperature.
b
Chemoselectivity in the formation of monosubstituted quinone
References and notes
phenyl ethers (3a–j) as shown in Table 2 prompted us to further
study the reactivity of adjacent chlorine atom in compound 3 in
water and we, therefore, studied in situ one-pot reaction of 2,3-di-
chloro-1,4-naphthoquinone (1a) first with phenols (2) (step 1) and
after completion, in situ reaction with thiophenols, substituted
anilines, and phenol derivatives (step 2) as shown in Scheme 2.
Thus 2,3-hetero disubstituted products of 1,4-naphthoquinoe can
be synthesized in good to excellent yields in water (Table 6) using
laundry detergent (LD, washing powder) in comparison with the
disubstituted products synthesized in the presence of excess
methanol/ethanol18 or DMSO31 in the absence of water in two
steps.
It is noteworthy that the in situ reaction with substituted ani-
lines and thiophenols (in step 2) is chemoselective. However, the
reverse process to synthesize in situ products 8 by reaction of ani-
line with quinone 1 (step 1) followed by reaction with phenol (2a)
(step 2) does not lead to the desired product by in situ one-pot syn-
thesis of 8.
In conclusion, we are the first to report the synthesis of the qui-
none phenyl ethers in water using low cost and economically via-
ble laundry detergent (LD, washing powder) as well as SDS as
surfactant. Results in laundry detergent (LD, washing powder)
are further being explored for various base-catalyzed reactions
which will be cost effective compared to other surfactants for var-
ious synthetic applications.9
Further work is in progress to explore ‘in water’ nucleophilic
substitution reactions for industrial applications and substituted
quinones with other nucleophiles.
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Acknowledgment
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H.K.M. acknowledges CSIR, New Delhi, India, for the Senior
Research Fellowship (extended) as project no-01(2280)/08/EMR-II.