Reaction under ball-milling: Solvent-, ligand-, and metal-free synthesis of unsymmetrical diaryl chalcogenides

Article abstract of DOI:10.1021/jo402071b

A convenient, efficient, and general procedure for the synthesis of diaryl chalcogenides including sulfides, selenides and tellurides has been developed by the reaction of diazonium tetrafluoroborates and diaryl dichalcogenides on the surface of alumina u

Full text of DOI:10.1021/jo402071b

Note
pubs.acs.org/joc
Reaction under Ball-Milling: Solvent‑, Ligand‑, and Metal-Free
Synthesis of Unsymmetrical Diaryl Chalcogenides
Nirmalya Mukherjee, Tanmay Chatterjee, and Brindaban C. Ranu*
Department of Organic Chemistry, Indian Association for the Cultivation of Science, Jadavpur, Kolkata-700032, India
S
* Supporting Information
ABSTRACT: A convenient, efficient, and general procedure for the synthesis
of diaryl chalcogenides including sulfides, selenides and tellurides has been
developed by the reaction of diazonium tetrafluoroborates and diaryl
dichalcogenides on the surface of alumina under ball-milling without any
solvent or metal. A wide range of functionalized diaryl chalcogenides are
obtained in high purity by this procedure.
n recent times ball-milling (intense mechanical grinding) is
of considerable interest as a greener tool for effecting a
reported15d a transition-metal-free reaction of substituted
benzene and diaryl dichalcogenides under oxidative condition
using potassium persulfate in trifluoroacetic acid at room
temperature (80 °C in few reactions) for 8−16 h to produce
aryl chalcogenides. This procedure too involved highly
corrosive and toxic trifluoroacetic acid and long reaction time.
Recently, we reported17 a microwave-assisted reaction of aryl
diazonium tetrafluoroborates and diaryl dichalcogenides in
dimethyl carbonate in the presence of zinc dust. In conven-
tional heating at 80 °C, the reaction required 8−10 h. For
further improvement we report here a solvent- and metal-free
reaction of aryl diazonium tetrafluoroborate and diaryl
dichalcogenides under ball-milling at ambient temperature for
the synthesis of unsymmetrical aryl chalcogenides (Scheme 1).
I
chemical transformation.1 A variety of reactions involving
carbon−carbon coupling,2 carbon−heteroatom bond forma-
tion,3 oxidation,4 and hydrogenation5 among others6 have been
efficiently performed by ball-milling. Currently we are also
actively engaged in exploring useful chemical transformations
under ball-milling.7 As a part of our continuing program we
report here another application of ball-milling for the synthesis
of unsymmetrical diaryl chalcogenides.
The aryl chalcogenides are of much importance and
continued interest because of their presence as structural
motifs in a variety of molecules of biological, pharmaceutical,
and material interest.8 Moreover, they are employed as useful
intermediates in organic synthesis.9 Thus, a number of methods
have been developed for their synthesis.10 One of the most
common and efficient practices is the transition-metal-mediated
aryl-chalcogen bond formation. Several metals including
palladium,11 nickel,12 copper,13 and iron14 have been employed
to catalyze the reaction of aryl halides/boronic acids with aryl
thiols/selenols/diselenides/ditellurides to achieve the synthesis
of the diaryl chalcogenides. Usually, diaryl dichalcogenides
being stable and readily available are preferred over foul
smelling thiol and less stable and more toxic selenols as
chalcogenating agents. However, reaction of diaryl dichalcoge-
nides and aryl halides/boronic acids requires a reductant for the
generation of chalcogenide anion and a transition metal for
subsequent carbon-chalcogen bond formation. Usually a metal
such as Zn or In is used as reducing agent, or a strong base is
used for the cleavage of dichalcogenides. In recent times a
metal-free reaction is of much interest as it avoids loss of
expensive metals and prevents environment pollution due to
toxicity of metal salts. A few metal-free procedures involving the
reactions of diazonium salts and lithium, sodium, or potassium
salts of arene thiolate/selnolate/tellurolate have also been
reported.15a−c However, these reactions use hazardous solvents
such as acetonitrile and DMSO, and the arene selenolate and
tellurolates are also toxic.16 Very recently Kumar et al.
Scheme 1. Synthesis of Unsymmetrical Functionalized Aryl/
Alkyl/Heteroaryl Chalcogenides
To optimize the reaction conditions for thiolation, a series of
experiments were performed for a representative reaction of 4-
methoxydiazonium tetrafluoroborate and di-4-chlorodiphenyl
disulfide with variation of grinding auxiliary, base, and time. All
three types of alumina and silica gel were tested as grinding
auxiliary, and it was found that neutral and basic alumina in
presence of 0.75 equiv of KOH worked most efficiently (Table
1, enries 8 and 12). Use of other milder bases such as K2CO3
Received: September 18, 2013
© XXXX American Chemical Society
A
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Note
Table 1. Optimization of Reaction Parameters for the
Reaction of Diazonium Tetrafluoroborate and Diaryl
Disulfide
Table 2. Synthesis of Unsymmetrical Diaryl or Aryl-Alkyl
Sulfides by Ball-Milling
entry
grinding auxiliary
base (equiv)
time (min)
yield (%)
1
neutral Al2O3
neutral Al2O3
neutral Al2O3
neutral Al2O3
neutral Al2O3
neutral Al2O3
neutral Al2O3
neutral Al2O3
neutral Al2O3
neutral Al2O3
neutral Al2O3
basic Al2O3
Cs2CO3 (3)
K2CO3 (3)
NaOH (3)
NaOH (1)
NaOH (0.75)
KOH (3)
15
15
15
15
15
15
15
15
15
10
15
15
15
15
15
0
0
2
3
68
78
83
78
85
4
5
6
7
KOH (1)
a
8
KOH (0.75)
KOH (0.5)
KOH (0.75)
KOH (0)
90
9
83
68
0
10
11
12
13
14
15
KOH (0.75)
KOH (0)
90
0
basic Al2O3
acidic Al2O3
silica
KOH (0.75)
KOH (0.75)
24
21
a
Best condition.
and Cs2CO3 did not yield satisfactory results; however, the
stronger base NaOH provided comparable yields as with KOH
(Table 1, entry 5). It was observed that in place of ball-milling,
stirring the reaction mixture by a magnetic stirrer did not
provide any product. Thus in a typical general procedure a
mixture of diazonium tetrafluoroborate (1 mmol), diaryl
disulfide (0.5 mmol), and KOH (0.75 mmol) on neutral
alumina (3 g) was ball-milled at 600 rpm using 6 balls for 15−
30 min (TLC). Extraction of product by elution with ethanol or
ethyl acetate followed by short column chromatography
provided the pure product. This procedure is also effective
for reactions with diaryl diselenides and ditellurides. Several
diversely substituted diazonium tetrafluoroborates underwent
reactions with diphenyl disulfides by this procedure to produce
the corresponding sulphides. The results are summarized in
Table 2. The substitution of electron-withdrawing and electron-
donating groups on the phenyl ring of diazonium fluoroborate
and disulfides did not have any appreciable influence on the
outcome of the reaction. Several functional groups such as
OCH3, COCH3, CF3, NO2, Cl, and Br are compatible with
these reaction conditions. The heterocyclic disulfide pyridinyl
disulfide also underwent reaction without any difficulty (Table
2, entry 2) to provide the corresponding aryl heteroaryl sulfide.
The aryl-alkyl sulphides were also obtained successfully by the
reaction of aryl diazonium fluoroborate and dialkyl disulfides
(Table 2, entries 5−8). The sterically hindered disulfide di-(2,6-
dimethylphenyl) disulfide also underwent reaction with 2-
bromophenyl diazonium fluoroborate successfully (Table 2,
entry 9).
a
Denotes the earlier reference of the corresponding product. Reaction
conditions: A mixture of diazonium salt (1 mmol), disulfane (0.5
mmol), KOH (0.75 mmol), and neutal alumina (3 g) was ball-milled
at 600 rpm.
in Table 4 for tellurides. The synthesis of a sterically hindered
selenide was also achieved by this procedure (Table 3, entry 2).
This procedure is also effective for the solvent-free synthesis
of S-aryl dithiocarbamates by the reaction of aryl diazonium
fluoroborate, carbon disulfide, and an amine. A variety of
functionalized dithiocarbamates were obtained. The results are
reported in Table 5. Cyclic amines such as thiomorpholine,
morpholine, pyrrolidine, and piperidine and the acyclic amine
dimethyl amine are compatible under this condition. This
procedure provides more advantages such as use of no solvent
and faster reaction (15−20 min) compared to our earlier
method running the reaction in water for 3−4 h.18j
The same procedure was followed for the reactions with
diphenyl diselenide and diphenyl ditelluride. Several unsym-
metrical functionalized diaryl selenides and tellurides were
obtained. The results are reported in Table 3 for selenides and
In general, the reactions are clean and high yielding. The only
byproduct formed is the corresponding phenol (2−5%), which
B
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Table 3. Synthesis of Unsymmetrical Diaryl Selenides by
Ball-Milling
Table 4. Synthesis of Unsymmetrical Diaryl Tellurides by
Ball-Milling
a
Denotes the earlier reference of the corresponding product. Reaction
conditions: A mixture of diazonium salt (1 mmol), ditelluride (0.5
mmol), KOH (0.75 mmol), and neutral alumina (3g) was ball-milled
at 600 rpm.
temperature, and use of stable and readily available diaryl
dichalcogenide in place of foul smelling and toxic thiols/
selenols/thiolate/selenoate makes this procedure a greener,
cost-effective, and better alternative to existing ones. Moreover,
this demonstrates the potential of ball-milling for clean organic
synthesis.
a
Denotes the earlier reference of the corresponding product. Reaction
condtions: A mixture of diazonium salt (1 mmol), diselenide (0.5
mmol), KOH (0.75 mmol), and neutral alumina (3g) was ball-milled
at 600 rpm.
EXPERIMENTAL SECTION
General. A PM 100, Retsch GmbH Germany, ball-milling
apparatus was used for all reactions. HRMS analysis was performed
in a QTOF mass analyzer using the ESI ionization method.
■
is easily separated out during column chromatography. Ball-
milling made the reactions remarkably faster. The nature and
position of substituents did not have any effect on the reaction
rates and yields. The chalcogenides are obtained pure and are
characterized properly by spectroscopic data. Several of these
products are new. Ball-milling makes this protocol proceed in
the absence of any metal, ligand, or solvent at ambient
temperature. It is predicted that the reaction proceeds through
an interaction of the chalcogenide anion, formed by the
cleavage of dichalcogenides in presence of KOH, with the
diazonium fluoroborate to provide the product via release of
nitrogen by a usual mechanism.17
In conclusion, we have developed a general procedure for the
synthesis of unsymmetrical diaryl chalcogenides (sulphides,
selenides, and tellurides) by a reaction of aryl diazonium
tetrafluoroborates and diaryl dichalcogenides under ball-milling
on the surface of alumina without requirement of any metal,
ligand, or solvent. To best of our knowledge this is the first
report of such synthesis involving diaryl dichalcogenides in the
absence of any metal and solvent under ball-milling. In
addition, the simplicity in operation, general applicability to
all three chalcogenides and S-aryl dithiocarbamates, scope of
functionalization, remarkably short reaction time at ambient
General Procedure for the Synthesis of Diaryl/Aryl-
Heteroaryl Sulfides. Representative Experimental Procedure
for the Synthesis of (4-Chlorophenyl)-(4-methoxyphenyl)
Sulfane (Table 2, Entry 1). A mixture of 4-methoxy diazonium
tetrafluoroborate (272 mg, 1 mmol), 1,2-bis(4-cholorophenyl)
disulfane (143.6 mg, 0.5 mmol), and KOH (42 mg, 0.75 mmol)
adsorbed on neutral alumina (3 g) was ball-milled in a 25 mL stainless
steel beaker with six balls (d = 10 mm) of the same material at 600
rpm for 15 min (Caution: The diazonium salts are, in general,
susceptible to explosion on heating/grinding, although we did not
encounter any such incidence during our investigation. However the
reactions should be performed in a closed fume cupboard.). The ball-
milling operation was performed using inverted rotation directions,
with an interval of 10 min and taking an interval break of 30 s.
Extraction of the reaction residue by simple elution with ethanol or
ethyl acetate followed by evaporation of the solvent gave the crude
product, which was purified by a short column chromatography over
silica gel (60−120 mesh) using a 9:1 hexane/diethyl ether mixed
solvent as eluant to give (4-chlorophenyl)-(4-methoxyphenyl) sulfane
1
as a white solid (225 mg, 90%); mp 60−62 °C; H NMR (300 MHz,
CDCl3) δ 3.83 (s, 3H), 5.90 (d, J = 9 Hz, 2H), 7.08 (d, J = 6 Hz, 2H),
7.19 (d, J = 9 Hz, 2H), 7.40 (d, J = 9 Hz, 2H); 13C NMR (75 MHz,
CDCl3) δ 55.5, 115.2 (2C), 123.8, 129.1 (2C), 129.4 (2C), 131.7,
C
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Note
7.26−7.36 (m, 4H), 8.16−8.21 (m, 2H); 13C NMR (75 MHz, CDCl3)
δ 25.7, 28.1, 33.5, 68.3, 114.5 (2C), 126.0 (2C), 126.2, 129.1 (2C),
129.5 (2C), 136.4, 141.6, 164.1. Anal. Calcd for C16H17NO3S: C,
63.34; H, 5.65; N, 4.62. Found: C, 63.39; H, 5.69; N, 4.66.
(2-Bromophenyl)-(2,6-dimethylphenyl) Sulfane (Table 2,
Entry 9). White solid (205 mg, 70%); mp 70−73 °C; IR (KBr)
3747, 3055, 3010, 2970, 2951, 2920, 2731, 1940, 1574, 1556, 1543,
1522, 1458, 1441, 1375, 1246, 1163, 1103, 1015 cm−1; 1H NMR (500
MHz, CDCl3) δ 2.41 (s, 6H), 6.34 (d, J = 8.5 Hz, 1H), 6.92−6.94 (m,
1H), 7.01 (t, J = 4 Hz, 1H), 7.21 (d, J = 10 Hz, 2H), 7.26−7.27 (m,
1H), 7.51 (d, J = 7 Hz, 1H); 13C NMR (75 MHz, CDCl3) δ 21.8 (2C),
122.7, 125.4, 125.7, 127.8 (2C), 128.2, 128.8 (2C), 129.9, 133.4, 139.2,
144.3. Anal. Calcd for C14H13BrS: C, 57.35; H, 4.47. Found: C, 57.38;
H, 4.45.
Table 5. Synthesis of S-Aryl Dithiocarbamates by Ball-
Milling
General Procedure for the Synthesis of Diaryl Selenides.
Representative Experimental Procedure for the Synthesis of
(4-Methoxyphenyl)-(phenyl) Selane (Table 3, Entry 1). A
mixture of 4-methoxy diazonium tetrafluoroborate (272 mg, 1
mmol), diphenyl diselenide (156 mg, 0.5 mmol), and KOH (42 mg,
0.75 mmol) adsorbed on neutral alumina (3g) was ball-milled as in
earlier procedure. Extraction and purification as mentioned earlier
provided the product as a colorless oil (205 mg, 78%); 1H NMR (500
MHz, CDCl3) δ 3.72 (s, 1H), 6.77 (d, J = 8.5 Hz, 2H), 7.09−7.16 (m,
3H), 7.25 (d, J = 5 Hz, 2H), 7.43 (d, J = 8.5 Hz, 2H); 13C NMR (125
MHz, CDCl3) δ 55.4, 115.3 (2C), 120.1, 126.6, 129.3 (2C), 131.0
(2C), 133.3, 136.6 (2C), 159.9. This compound is identified as (4-
methoxyphenyl)-(phenyl) selane by comparison of its spectroscopic
data with those reported earlier.18f
This procedure was followed for all of the reactions in Table 3. All
of these products are known compounds (see the references in Tables
3) and were easily identified by comparison of their spectroscopic data
with those previously reported.
General Procedure for the Synthesis of Diaryl Tellurides.
Representative Experimental Procedure for the Synthesis of
(4-Methoxyphenyl)-(phenyl) Tellane (Table 4, Entry 1). A
mixture of 4-methoxy diazonium tetrafluoroborate (272 mg, 1
mmol), diphenyl ditelluride (200 mg, 0.5 mmol), and KOH (42 mg,
0.75 mmol) adsorbed on neutral alumina (3 g) was ball-milled under
the same conditions as earlier. Extraction and purification of the
reaction residue provided the product, (4-methoxyphenyl)-(phenyl)
tellane, as a white solid (236 mg, 76%); mp 60−62 °C; 1H NMR (300
MHz, CDCl3) δ 3.80 (s, 3H), 6.78−6.81 (m, 2H), 7.16−7.20 (m, 3H),
7.55−7.58 (m, 2H), 7.71−7.74 (m, 2H); 13C NMR (75 MHz, CDCl3)
δ 55.3, 103.4, 115.7 (2C), 127.4, 129.5 (2C), 136.6 (2C), 136.7, 141.3
(2C), 160.2. These data are in agreement with those reported
earlier.18h
a
Denotes the earlier reference of the corresponding product. Reaction
conditions: CS2 (2.5 mmol) and amine (1.2 mmol) were added
dropwise to neutral alumina (3 g) at 0−5 °C and subjected to ball-
milling at 600 rpm for 2 min. Diazonium salt (1 mmol) was added and
further ball-milled at 600 rpm.
This procedure was followed for all of the reactions in Table 4.
Almost all of these products are known compounds (see the references
in Table 4) and are easily identified by comparison of their
spectroscopic data with those previously reported. The unknown
135.5 (2C), 137.5, 160.2. These data are in good agreement with those
of an authentic sample reported earlier.18a
1
This procedure was followed for all of the reactions listed in Table
2. Almost all of these products are known compounds (see the
references in Table 2) and were easily identified by comparison of
their spectroscopic data with those previously reported. The unknown
compound (Table 4, entry 5) was characterized by its IR and H and
13C NMR spectroscopic data and elemental analysis. These data are
given below.
(3-Chloro-4-methylphenyl)-(phenyl) Tellane (Table 4, Entry
5). Brown viscous oil (251 mg, 76%); IR (neat) 3049, 2951, 2922,
2850, 1574, 1545, 1471, 1435, 1363, 1051 cm−1; 1H NMR (300 MHz,
CDCl3) δ 2.36 (s, 3H), 7.05−7.08 (m, 1H), 7.20−7.30 (m, 3H),
7.45−7.49 (m, 1H), 7.68−7.70 (m, 3H); 13C NMR (75 MHz, CDCl3)
δ 20.0, 112.0, 114.6, 128.2, 129.7, 132.0, 132.1, 135.4, 136.4, 136.5
(2C), 138.1 (2C). Anal. Calcd for C13H11ClTe: C, 47.27; H, 3.36.
Found: C, 47.21; H 3.39.
General Procedure for the Synthesis of S-Aryl Dithiocarba-
mate. Representative Experimental Procedure for the Syn-
thesis of 4-Methoxyphenyl Thiomorpholine-4-carbodithioate
(Table 5, Entry 1). A mixture of carbon disulfide (190 mg, 2.5 mmol)
and thiomorpholine (124 mg, 1.2 mmol) was added dropwise to
neutral alumina (3 g) in the ball-milling stainless steel beaker (25 mL)
kept at 0−5 °C (at this stage the beaker remained outside the ball-mill
machine), and the beaker containing the reaction mixture was then
subjected to ball-milling with six balls (d = 10 mm) at 600 rpm for 2
min. 4-Methoxy diazonium tetrafluoroborate (272 mg, 1 mmol) was
1
compounds were characterized by their IR and H and 13C NMR
spectroscopic data and HRMS or elemental analysis. These data are
given below in the order of their entries in Table 2.
(4-Methoxyphenyl)-(octadecyl) Sulfane (Table 2, Entry 7).
Dirty white solid (282 mg, 72%); mp 64−66 °C; IR (KBr) 2955, 2918,
2849, 1726, 1498, 1464, 1288, 1247, 1220, 1180, 1120, 1029 cm−1; 1H
NMR (500 MHz, CDCl3) δ 0.86−0.93 (m, 3H), 1.25−1.29 (m, 28H),
1.34−1.39 (m, 2H), 1.56−1.60 (m, 2H), 2.80 (t, J = 7.5 Hz, 2H), 3.79
(s, 3H), 6.83 (d, J = 8.5 Hz, 2H), 7.33 (d, J = 8.5 Hz, 2H); 13C NMR
(125 MHz, CDCl3) δ 14.2, 22.8, 28.9, 29.0, 29.3, 29.5, 29.6, 29.7 (8C),
29.8, 32.0, 36.0, 55.5, 114.6 (2C), 127.2, 133.0 (2C), 158.9. Anal.
Calcd for C25H44OS: C, 76.47; H, 11.29. Found: C, 76.42; H, 11.25.
(4-(4-Nitrophenoxy)butyl)-(phenyl) Sulfane (Table 2, Entry
8). White solid (221 mg, 73%); mp 92−94 °C; IR (KBr) 2920, 2850,
1593, 1510, 1340, 1298, 1261, 1172, 1111 cm−1; 1H NMR (300 MHz,
CDCl3) δ 1.79−1.89 (m, 2H), 1.94−2.04 (m, 2H), 3.0 (t, J = 11.5 Hz,
2H), 4.06 (t, J = 10 Hz, 2H), 6.89−6.94 (m, 2H),7.16−7.21 (m, 1H),
D
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Note
added, and the reaction mixture was further subjected to ball-milling
for 15 min as earlier. Extraction and purification of the reaction
mixture in the same way as mentioned earlier provided the product, 4-
methoxyphenyl thiomorpholine-4-carbodithioate, as a pale yellow solid
(245 mg, 86%); mp 122−125 °C ; IR (KBr) 2955, 2924, 2852, 1736,
1591, 1493, 1464, 1439, 1410, 1290, 1250, 1172, 1030 cm−1; 1H NMR
(400 MHz, CDCl3) δ 2.80 (t, J = 6 Hz, 4H), 3.85 (s, 3H), 4.42−4.57
(broad, 4H), 6.95−6.97 (m, 2H), 7.36−7.38 (m, 2H); 13C NMR (75
MHz, CDCl3) δ 54.3 (2C), 55.4, 60.5 (2C), 114.9 (2C), 121.8, 138.7
(2C), 161.3, 198.7. Anal. Calcd for C12H15NOS3: C, 50.49; H, 5.30; N,
4.91. Found: C, 50.43; H, 5.35; N, 4.94.
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This procedure was followed for all of the reactions in Table 5. A
few of these products are known compounds (see the references in
Table 5) and were easily identified by comparison of their
spectroscopic data with those previously reported. The unknown
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1
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HRMS spectroscopic data. These data are given below in order of their
entries in Table 5.
4-Nitrophenyl Pyrrolidine-1-carbodithioate (Table 5, Entry
4). Pale yellow gummy oil (207 mg, 77%) ; IR (neat) 3096, 2970,
2949, 2922, 2868, 2847, 1597, 1574, 1518, 1472, 1433, 1392, 1337,
1281, 1250, 1221, 1178, 1153, 1105, 1078 cm−1; 1H NMR (500 MHz,
CDCl3) δ 2.02−2.06 (m, 2H), 2.14−2.19 (m, 2H), 3.80−3.86 (m,
2H), 3.91−3.99 (m, 2H), 7.68 (d, J = 7 Hz, 2H), 8.26 (d, J = 7 Hz,
2H); 13C NMR (125 MHz, CDCl3) δ 24.4, 26.5, 51.0, 55.6, 123.9
(2C), 137.6 (2C), 139.1, 148.8, 190.1. HRMS calcd for C11H12N2O2S2
[M + H]+ 269.0413, found 269.0391.
Naphthalene-5-yl 4-Methyl piperidine-1carbodithioate
(Table 5, Entry 5). Yellow viscous oil (241 mg, 80%); IR (neat)
3053, 2988, 2949, 2924, 2868, 2849, 1558, 1502, 1473, 1429, 1379,
1364, 1304, 1263, 1225, 1192, 1138, 1082, 1020 cm−1; 1H NMR (500
MHz, CDCl3) δ 1.03 (d, J = 6 Hz, 3H), 1.40 (s, 2H), 1.76−1.80 (m,
3H), 3.12 (s, 1H), 3.39 (s, 1H), 4.87 (s, 1H), 5.44 (s, 1H), 7.49−7.56
(m, 3H), 7.75−7.80 (m, 1H), 7.84−7.89 (m, 1H), 7.98 (d, J = 8.5 Hz,
1H), 8.24 (d, J = 8 Hz, 1H); 13C NMR (125 MHz, CDCl3) δ 21.4,
31.0, 33.6, 34.2, 51.4, 52.2, 125.8, 126.0, 126.4, 127.3, 128.7, 129.1,
131.5, 134.3, 135.4, 137.2, 195.3. HRMS calcd for C17H19NS2 [M +
H]+ 302.1032, found 302.1016.
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ASSOCIATED CONTENT
■
S
* Supporting Information
Copies of 1H NMR and 13C NMR spectra of all products listed
in Tables 2−5. This material is available free of charge via the
Internet at http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
*E-mail: ocbcr@iacs.res.in.
■
(16) Snyder, R. D. Cancer Lett. 1987, 34, 73.
(17) Kundu, D.; Ahammed, S.; Ranu, B. C. Green Chem. 2012, 14,
2024.
Notes
The authors declare no competing financial interest.
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ACKNOWLEDGMENTS
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We are pleased to acknowledge financial support from CSIR,
New Delhi (Grant no. 01 (2365)/10/EMR-II) and DST for the
award of a J C Bose Fellowship to B.C.R. T.C. thanks CSIR for
his fellowships.
REFERENCES
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