Copper MOF: Scope and limitation in catalytic hydroxylation and nitration of aryl halides

Article abstract of DOI:10.1016/j.tet.2013.05.102

The potential catalytic application of MOFs like [Cu₃(btc) ₂] (btc=1,3,5-benzenetricarboxylate), [Cu(bdc)] (bdc=1,4- benzenedicarboxylate), [Cu(pymo)₂] (pymo=2-hydroxypyrimidinalote) and [Cu(im)₂] (im=imidazolate) was explored in the hydroxylation and nitration of aryl halides. Cu₃(btc)₂ was found to be superior for both the reactions furnishing good to excellent yields of the respective products. The studies demonstrated that MOFs are not recyclable, attributable to their instability in the highly polar and basic conditions demanded for these reactions. Complete transformation of MOFs to copper oxide nanoparticles occurred in hydroxylation, whereas significant alteration in frameworks was observed for the recovered catalyst in nitration.

Full text of DOI:10.1016/j.tet.2013.05.102

Accepted Manuscript
Copper MOF: Scope and limitation in catalytic hydroxylation and nitration of aryl
halides
S. Priyadarshini, P.J. Amal Joseph, M. Lakshmi Kantam, B. Sreedhar
PII:
S0040-4020(13)00858-2
10.1016/j.tet.2013.05.102
TET 24440
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 12 January 2013
Revised Date: 18 May 2013
Accepted Date: 22 May 2013
Please cite this article as: Priyadarshini S, Amal Joseph PJ, Lakshmi Kantam M, Sreedhar B, Copper
MOF: Scope and limitation in catalytic hydroxylation and nitration of aryl halides, Tetrahedron (2013),
doi: 10.1016/j.tet.2013.05.102.
This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to
our customers we are providing this early version of the manuscript. The manuscript will undergo
copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please
note that during the production process errors may be discovered which could affect the content, and all
legal disclaimers that apply to the journal pertain.

ACCEPTED MANUSCRIPT
Graphical Abstract
To create your abstract, type over the instructions in the template box below.
Fonts or abstract dimensions should not be changed or altered.
Copper MOF: Scope and limitation in
catalytic hydroxylation and nitration of aryl
halides
Leave this area blank for abstract info.
S. Priyadarshini, P. J. Amal Joseph, M. Lakshmi Kantam* and B. Sreedhar
The potential application of copper MOFs as catalyst for coupling reactions was demonstrated in hydroxylation
and nitration of aryl halides

ACCEPTED MANUSCRIPT
1
Tetrahedron
journal homepage: www.elsevier.com
Copper MOF: Scope and limitation in catalytic hydroxylation and nitration of aryl
halides
S. Priyadarshinia, P. J. Amal Josepha, M. Lakshmi Kantama, *and B. Sreedhara
aInorganic and Physical Chemistry Division, CSIR-Indian Institute of Chemical Technology, Hyderabad – 500607, INDIA, Fax: +91-40-27160921;
E-mail: mlakshmi@iict.res.in
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
The potential catalytic application of MOFs like [Cu3(btc)2] (btc = 1,3,5-benzenetricarboxylate),
[Cu(bdc)] (bdc = 1,4-benzenedicarboxylate), [Cu(pymo)2] (pymo = 2-hydroxypyrimidinalote),
and [Cu(im)2] (im = imidazolate) were explored in the hydroxylation and nitration of aryl
halides. Cu3(btc)2 was found to be superior for both the reactions furnishing good to excellent
yields of the respective products. The studies demonstrated that MOFs are not recyclable,
attributable to their instability in the highly polar and basic conditions demanded for these
reactions. Complete transformation of MOFs to copper oxide nanoparticles occurred in
hydroxylation, whereas significant alteration in frameworks was observed for the recovered
catalyst in nitration.
Available online
Keywords:
Metal organic framework
Hydroxylation
Nitration
Aryl halides
Phenols
2009 Elsevier Ltd. All rights reserved.
1. Introduction
solvent medium. However, these paradoxes in hydroxylation
were resolved by pertinent solvent choice, employing
Phenols and nitroarenes are prevalent building blocks as well
as important structural constituents that are present in numerous
DMSO/H2O system. Several homogenous catalytic systems
based on both copper7 and palladium8 complexes have been
reported for the hydroxylation of aryl halides with hydroxide
salts. In contrast, analogous preparation of nitroarenes through
catalytic C-N bond formation of aryl halides with nitrite salts is
not well established as nitrite anion is a comparatively low
carbon base attacking through its nitrogen atom than by its
oxygen atom.9-11
natural
products,
biologically
active
compounds,
pharmaceuticals, agrochemicals, polymers, dyes, explosives and
materials.1 These functionalities have dominant role in organic
synthesis due to the broad spectrum of organic reactions and
transformations they can undergo. Several valuable functional
moieties like diaryl ethers, alkyl aryl ethers, aryl triflates, aryl
aldehydes and aryl amines are prepared from these compounds.2,3
Recently, direct methods for the synthesis of phenols and
nitroarenes through ipso-substitution of aryl halides have gained
much attention attributable to the concepts of atom economy,
ready availability and low cost of aryl halides.4 An added
advantage of these processes is in their exceptional
regioselectivity, high yields and mild conditions.
In recent years, there has been remarkable progress in the
design and the use of metal organic frameworks as catalysts, and
also in various applications such as separations, gas storage,
chemical sensors and controlled drug delivery due to their innate
advantages such as high porosity and high specific surface
area.12,13 It is noteworthy that many significant features like
shape, size, and properties of these crystalline materials can be
manipulated by altering the nature of metal ion and organic
linkers, thereby providing tremendous opportunities to synthesize
several classes of novel materials. MOFs resemble zeolites in
crystallinity and homogeneous active sites. However; unlike
zeolites, the direct synthesis of MOFs can be performed easily
without any additional templates. Although, there is enormous
potential for catalytic application of MOFs, still this field is in
infancy attributed to its relatively low thermal and chemical
stability when compared to zeolites and mesoporous silica.
Phenols are typically synthesized by non-oxidative methods
involving nucleophilic aromatic substitution of activated aryl
halides, copper mediated conversion of diazoarenes, aryl boronic
acids and benzyne protocols.5 All these methods have drawbacks
either from the requirement of harsh reaction conditions, tedious
synthetic steps or non-availability of starting materials. On the
other hand, catalytic C-O bond formation of aryl halides with
hydroxide salts is a challenging process because of the relatively
high reactivity of the initially formed phenol with the remaining
unreacted aryl halides to form symmetrical diarylethers.6 An
additional persistent problem encountered for this reaction is
concerning the mutual solubility of the aryl halide and
nucleophile, which is often an alkali metal hydroxide, in the
Recently, MOFs were successfully used as catalysts for
several reactions like oxidation,14 hydrogenation,15 epoxidation,16
cycloproponation,17 ring opening reaction,18 cyanosilylation,19

ACCEPTED MANUSCRIPT
2
Tetrahedron
10d
11e
12f
13
Cu3(btc)2
Cu3(btc)2
Cu3(btc)2
DMSO/H2O KOH
DMSO/H2O KOH
72
20
0
Friedel-Crafts
Friedlander
reaction,20
reaction,22
Knoevenagel
acetalization,
condensation,21
N-alkylation,
polymerization etc under mild conditions.23 However, their
direct applications in ipso-substitution of aryl halides (C-N, C-O
and C-S bond formations) are hardly explored.24 Therefore, to
demonstrate the utility of MOFs as catalysts in these reactions,
we have chosen two important reactions as examples; i.e.,
hydroxylation and nitration of aryl halides. Since, copper(II) salts
were known to catalyze these reactions under homogenous
conditions, it was conceived that Cu MOFs can also be used as
catalysts due to their broad similarity.7g,10d,12a,b Notably, the
application of copper MOFs as catalysts for C-O and C-N bond
formation reaction of aryl halides are unique, the details of these
observations is the focus of this paper.25
H2O
KOH
CuO nano particles DMSO/H2O KOH
62
68
10
85
14
CuO recovered
CuO commercial
CuO recovered
DMSO/H2O KOH
DMSO/H2O KOH
DMSO/H2O KOH
15
16g
a Unless otherwise stated, all the reactions were performed with 4-iodoanisole
(1 mmol), base (4 equiv) and catalyst (~10 mol % of Cu) in 1.6 mL of 1:1
DMSO/H2O for 12 h at 125 oC.
b Isolated yield.
c
2.5 mL of 40 wt % tetrabutylammonium hydroxide (TBAOH) in water
(contains ~1.5 mL of water) and 1.5 mL of DMSO was used.
d DMSO/H2O ratio was 2:1.
2. Results and Discussion
e DMSO/H2O ratio was 1:2.
To begin with, 4-iodoanisole was selected as a model
substrate for hydroxylation, and was subjected to various reaction
conditions using copper MOF as catalyst and base in 1:1
f H2O was used as solvent.
g Reaction performed with added trimesic acid (10 mol %).
o
DMSO/H2O at 125 C. The results of these studies are presented
in Table 1. As seen in Table 1, MOFs such as [Cu3(btc)2] (btc =
1,3,5-benzenetricarboxylate); see supplementary content,
[Cu(bdc)] (bdc = 1,4-benzenedicarboxylate), [Cu(pymo)2] (pymo
= 2-hydroxypyrimidinalote), and [Cu(im)2] (im = imidazolate)
catalyzed the reaction in good to excellent yields (Table 1, entries
1-4). However, very poor results were obtained with copper
precursors like CuI, Cu(OAc)2 and commercial CuO (Table 1,
entries 5, 6 & 14). Among the bases screened good results were
obtained with alkali metal hydroxides. In contrast, very poor
yields were obtained when the reaction was performed using
TBAOH (Table 1, entry 9). It is important to note that the
reaction is sensitive to the amount and ratio of the solvent used.
For example, O-arylation of the product with the starting material
occurs significantly when the DMSO/water ratio is higher,
whereas hydroxylation failed in excess water (Table 1, entries
10-12). Thus among the various optimization studies listed in
Table 1 for the hydroxylation of 4-iodoanisole, the most
promising result was shown in entry 1.
Using the optimized conditions, several structurally diverse
aryl iodides were tested for hydroxylation. As presented in Table
2, various electron rich aryl iodides like 4-iodoanisole, 4-
iodotoluene, 4-t-butyl-iodobenzene, 4-iodothioanisole and 1-(4-
iodophenyl)-1H-pyrrole reacted smoothly to afford the
corresponding phenols in excellent yields (Table 2, entries 2-5, &
7). In a similar way, the reaction of electron deficient aryl iodides
also proceeded well (Table 2, entries 13 & 14). Furthermore,
sterically hindered aryl iodides like 2,6-dimethoxy-iodo-benzene
also reacted well to provide the respective phenol in very good
yields (Table 2, entry 12). It is noteworthy that several functional
groups like NO2, COMe, OH, Cl, OMe, SMe, pyrrole were
tolerated in this protocol. However, sensitive substrates such as
4-iodobenzonitrile and 4-iodobenzaldehyde did not survive the
present conditions. Thereafter, the scope of this method was
checked for aryl bromides, aryl chlorides and heteroaryl halides.
The reaction of electron deficient aryl bromides proceeded
smoothly similar to their iodo counterparts to furnish the
corresponding phenols in excellent yields (Table 2, entries 15 &
16). In contrast, the reaction of electron rich aryl bromides like 4-
bromoanisole was sluggish and only poor yield of the product
was obtained (Table 2, entry 20). Notably, 4-chloronitrobenzene
reacted well to provide 4-nitrophenol in good yields, whereas the
reaction of 4-chloroacetophenone gave lower yields (Table 2,
entries 21 & 22). Later, heterocycles like 3-bromoquinoline, 6-
bromoquinoline, and 3-(4-bromophenyl)pyrimidine were utilized
successfully for hydroxylation (Table 2, entries 17-19).
Table 1
Optimization studies for hydroxylationa
Entry Catalyst
Solvent
Base
Yield (%)b
Table 2
1
2
3
4
5
6
7
8
9c
Cu3(btc)2
Cu(bdc)
Cu(pymo)2
Cu(im)2
Cu(OAc)2
CuI
DMSO/H2O KOH
DMSO/H2O KOH
DMSO/H2O KOH
DMSO/H2O KOH
DMSO/H2O KOH
DMSO/H2O KOH
DMSO/H2O NaOH
DMSO/H2O CsOH
94
90
92
75
8
Cu3(btc)2 catalyzed hydroxylationa
9
Entry
1
ArX
ArOH
Yield/%b
91
Cu3(btc)2
Cu3(btc)2
Cu3(btc)2
89
90
DMSO
TBAOH 10

ACCEPTED MANUSCRIPT
3
examined for nitration (C-N bond formation). For this,
2
94
optimization studies were carried out altering various parameters
such as catalyst, nucleophiles and solvents, using 4-
bromothioanisole as the model substrate in a 1 mmol scale at 130
oC (Table 3). The results revealed that Cu3(btc)2, KNO2, and
DMSO as the best catalyst, nucleophile and solvent respectively
(Table 3, entry 1). With the optimized conditions in hand, we
explored the reaction for various aryl iodides, aryl bromides, and
heteroaryl halides. As illustrated in Table 4, both electron
donating and electron withdrawing aryl iodides, aryl bromides
and heterocyclic aryl bromides reacted smoothly to furnish the
corresponding products in good yields. However; the protocol
failed to tolerate aryl halides containing amino or hydroxyl
functionalities. In a similar way, the reaction of aryl chlorides
and ortho-substituted aryl halides were sluggish and only trace
amount of products were obtained.
3
4
95
93
5
6
7
90
88
80
8
90
80
85
Table 3
9
Optimization studies for nitrationa
10
11
12
84
90
Entry Catalyst
Solvent Nucleophile Yield (%)b
1
Cu3(btc)2
Cu(bdc)
DMSO
DMSO
KNO2
KNO2
KNO2
KNO2
KNO2
KNO2
KNO2
NaNO2
AgNO2
TBANO2
82
80
66
23
62
trace
0
13
14
96, 28c
84
2
3
Cu3(pymo)2 DMSO
I
4
Cu(im)2
DMSO
DMSO
DMF
O
5
Cu(OAc)2
Cu3(btc)2
Cu3(btc)2
Cu3(btc)2
Cu3(btc)2
Cu3(btc)2
6
15
80
7
Xylene
DMSO
DMSO
DMSO
8
78
24
75
16
17
18
19
95, 32c
88
9
10
a
Reactions performed with 4-bromothioanisole (1 mmol), nucleophile (3
equiv) and catalyst (~30 mol % of Cu) in 1.2 mL solvent for 48 h at 130 oC.
b Isolated yield.
89
82
Table 4
Cu3(btc)2 catalyzed nitrationa
20d
21
22
a
24
95, 30c
28, 8c
Entry ArX
1
ArNO2
Yield/%b
82
Reaction performed in 1 mmol scale using aryl halides (1 mmol), KOH (4
equiv) and Cu3(btc)2 (20 mg, ~ 10 mol % of Cu) in 1.6 mL of 1:1 DMSO/H2O
at 125 oC for 12 h.
2
3
78
70
b Isolated yield.
c Reaction performed in absence of catalyst.
d Reaction performed at 130 oC.
4
80
Encouraged by the results obtained for hydroxylation (C-O
bond formation), it was comprehended that this protocol could be

ACCEPTED MANUSCRIPT
4
Tetrahedron
completion of the reaction, the catalyst was recovered by
5
6
7
66
60
48
centrifugation as a black powder and was well characterized by
XRD, XPS, TEM, UV-DRS and FT-IR spectroscopy (see Fig. 1
& 2, and supplementary data). As can be seen from the XRD
profile (Fig. 1), diffraction peaks obtained at 2θ values 32.53,
35.40, 38.72, 48.85, 53.52, 58.62 and 60.26o correspond to the
crystal planes of 110, 002, 111, 202, 020, 202 and 113 of
crystalline CuO respectively.26 This indicates that Cu3(btc)2 was
completely transformed into CuO during the reaction and the
TEM image (Fig. 2) clearly shows that the size of the particles is
10 nm. Moreover, the size of the crystallites as calculated from
the broadening of peak corresponding to the diffraction from 111
plane using Debye–Scherrer equation was found to be 8 nm
which is in consonance with the size of the nanoparticles
observed with TEM. These observations in the present study are
analogous to Garcia et al report concerning the chemical
instability of Cu3(btc)2 in the presence of thiols forming copper
nanoparticles.27 In addition, other MOFs like Cu(pymo)2 and
Cu(im)2 were also transformed to CuO, when employed as
catalysts in hydroxylation. This limits the reusability of MOFs
for catalytic hydroxylation of aryl halides. The formation of CuO
and potassium trimesate can be attributed to the reaction of
Cu3(btc)2 with KOH (Scheme 1).28 Next, to verify whether the
hydroxylation is indeed catalyzed by Cu3(btc)2 or by CuO, a
reaction was performed under standard conditions using
recovered CuO (formed from Cu3(btc)2 during hydroxylation);
see Table 1, entry 14. Notably, this reaction also yielded the
corresponding product, albeit in moderate yields. Similarly, a
reaction performed using trimesic acid and recovered CuO under
in situ conditions also furnished the product in excellent yields
(Table 1, entry 16). In addition, ICP OES analysis of the filtered
reaction solution (after 3 h from the start of reaction) revealed
that leaching is negligible (~1 %).29 Therefore, the reaction
demonstrated is to a certain extent heterogeneous in nature and
catalysis occurs in synergy through Cu3(btc)2 and its components
CuO/potassium trimesate, with the later system holding the major
contribution.30 Afterwards, the reusability of the catalyst was
examined for the nitration of 4-bromothioanisole. It is significant
to mention that ~75 % of catalyst was recovered from the
8
78
a
Reactions performed with aryl halides (1 mmol), KNO2 (3 equiv) and
Cu3(btc)2 (60 mg, ~30 mol % of Cu) in 1.2 mL DMSO for 48 h at 130 oC.
b Isolated yield.
reaction performed in
2 mmol scale under the standard
Fig. 1. XRD patterns of Cu3(btc)2: (a) fresh, (b) recovered (nitration), (c)
recovered (hydroxylation).
conditions. Analysis of the recovered catalyst using powder XRD
revealed that the framework is completely altered (Fig 1, see also
Fig 3 for SEM analysis); whereas, XPS analysis of the recovered
catalyst confirmed the +2 oxidation state of copper (see
supplementary data). In contrast, FT-IR spectra of the fresh and
used Cu3(btc)2 showed broad resemblance; although, additional
peaks appeared at 1568 and 1264 cm-1 in the recovered catalyst
may have orginated from NO3 group bounded to copper. The ICP
OES analysis of the filtrate obtained from the nitration reaction
mixture showed around ~20 % of copper leaching. This confines
the use of MOFs as heterogeneous catalyst for nitration of aryl
halides.
Fig. 2. TEM image of recovered catalyst in hydroxylation.
Scheme 1. Reaction of Cu3(btc)2 with KOH.
Later, to check the reusability of the catalyst for
hydroxylation, a reaction was performed in 2 mmol scale using
4-iodoanisole, KOH and Cu3(btc)2 in DMSO/H2O. After

ACCEPTED MANUSCRIPT
5
washed thoroughly with water and further with ethanol to
obtain Cu3(btc)2.3H2O. This compound was characterized by
XRD, IR and XPS. The compound was dried under high vacuum
at 100 oC overnight to obtain Cu3(btc)2, which was used
immediately.
4.2.2.
Synthesis
of
Cu(bdc).DMF
(bdc
=
1,4-
benzenedicarboxylate): Cu(bdc) was synthesized following the
reported procedure.32 An equimolar quantity of Cu(NO3)2 (1.053
g) and terephthalic acid (0.724 g) were dissolved in DMF (87
mL). This solution was placed in a closed scintillation flask in an
oven at 110 °C for 36 h. The blue precipitated crystals formed is
filtered and washed with DMF. It was activated by drying under
reduced pressure at 130 oC for 12 h to obtain Cu(bdc) which was
used immediately for the reaction.
Fig. 3. SEM images of fresh Cu3(btc)2 (left), and recovered Cu3(btc)2 from
nitration (right).
3. Conclusion
4.2.3. Synthesis of [Cu(pymo)2].2.25H2O (pymo
=
2-
In conclusion, we have demonstrated the application of copper
MOF as a catalyst for hydroxylation and nitration of aryl halides.
The studies prove that MOFs are highly unstable to the highly
basic and polar conditions demanded for hydroxylation resulting
in total destruction of framework forming copper oxide
nanoparticles. Significant alteration in framework was observed
for the recovered catalyst in nitration. Notably, irrespective of the
instability of MOFs to the nature of the reaction conditions, good
yields were obtained for both hydroxylation and nitration
reactions.
hydroxypyrimidinalote): The title compound was synthesized
following the reported procedure.33 An aqueous ammonia
solution (30 mL) containing CuCl2 (1 mmol) and 2-
hydroxypyrimidine.HCl (2 mmol) were kept in open air for 1 day
(pH 9.5). A dark purple solid obtained, was filtered, and washed
successively with water and ethanol, and later dried under high
vacuum at 100 oC before use.
4.2.4. Synthesis of Cu(im)2 (im = imidazolate): The synthesis
of Cu(im)2 was performed following the reported procedure as
follows.34 NaOH (0.1 M) was added dropwise to a solution
containing 2 g of imidazole (29.4 mmol) in 50 mL of 0.05 M
Cu(NO3)2.3H2O (2.50 mmol), till the formation of a reddish
purple precipitate was observed. The powder was recovered by
filtration, washed with ethanol and subsequently dried under high
vacuum at 100 oC overnight and stored under nitrogen
atmosphere. Anal. Calcd for CuC6H6N4: C, 36.45; H, 3.06; N,
28.34; Cu, 32.15. Found: C, 36.25; H, 3.14; N, 28.18; Cu, 32.40.
4. Experimental Section
4.1. General methods: All the chemicals were purchased from
either Sigma Aldrich or Alfa Aesar Company and are used as
received. The Thin Layer Chromatography (TLC) was performed
on Merck silica gel 60 F254 plates using ethyl acetate and hexane
as eluting agents. All hydroxylation reactions and MOFs
synthesis are carried out under air atmosphere. All nitration
reactions are carried out in nitrogen atmosphere. Purification of
products was carried out by column chromatography using silica
gel (100-200 mesh) and a mixture of ethyl acetate and hexane as
eluting agent. All products were characterized by 1H and 13C
NMR Spectroscopy. The NMR spectra of samples were acquired
on a Bruker Avance 300 MHz or Varian Unity Inova 500 MHz
spectrometer using TMS as an internal standard in CDCl3 or
DMSO-d6 as solvent. XPS spectra were recorded on a KRATOS
AXIS 165 equipped with Mg Kα radiation (1253.6 eV) at 75 W
apparatus using Mg Kα anode and a hemi spherical analyzer. The
C 1s line at 284.6 eV was used as an internal standard for the
correction of binding energies. The X-ray diffraction (XRD)
patterns of the fresh and used samples were obtained on a Rigaku
Miniflex X-ray diffractometer using Ni filtered Cu Kα radiation
(λ= 0.15406 nm), at a scan rate of 2°min−1, with the beam voltage
and beam current of 30 kV and 15 mA respectively. Elemental
Analysis of complexes was carried out on Elementar Vario-EL
CHNS analyzer. ICP OES analysis was performed on a Thermo
Intrepid XSP DUO instrument. Scanning electron micrograph
was acquired on a SEM Hitachi S520. Transmission electron
micrograph was acquired on Tecnai-12, FEI.
4.3.1. General procedure for hydroxylation of aryl halides:
An oven dried tube was charged with aryl halides (1 mmol),
Cu3(btc)2 (20 mg), KOH (224 mg, 4 mmol) and 1:1 DMSO/H2O
(1.6 mL). The tube was sealed with a teflon screw cap and stirred
at 125 oC for 12 h. The reaction mixture was then cooled to room
temperature, quenched with 2N HCl. Thereafter, it was washed
with excess ice cold water and extracted with ethyl acetate (3 x
10 mL). The combined organic extracts were dried over
anhydrous Na2SO4, filtered and concentrated under reduced
pressure to give the crude product which was purified by column
chromatography using silica gel and a mixture of ethyl acetate
and hexane as the eluent to afford the desired products in good
yields.
4.3.2. General procedure for nitration of aryl halides: An
oven dried tube was charged with aryl halides (1 mmol),
Cu3(btc)2(60 mg), KNO2 (265 mg, 3 mmol) and DMSO (1.2 mL)
under nitrogen atmosphere. The tube was sealed with a teflon
o
screw cap and stirred at 130 C for 48 h. The reaction mixture
was then cooled to room temperature, washed with excess ice
cold water and extracted with ethyl acetate (3 x 10 mL). The
combined organic extracts were dried over anhydrous Na2SO4,
filtered and concentrated under reduced pressure to give the
crude product which was purified by column chromatography
using silica gel and a mixture of ethyl acetate and hexane as the
eluent to afford the desired products in good yields.
4.2.1.
Synthesis
of
Cu3(btc)2
(btc
=
1,3,5-
benzenetricarboxylate): Cu3(btc)2 was synthesized according to
the method reported in the literature.31 A solution of 0.84 g of
trimesic acid and 1.75 g of Cu(NO3)2.3H2O in 50 mL of EtOH
was refluxed for 48 h under stirring. Thereafter, it was allowed to
cool to room temperature, and the blue precipitate formed was
filtered through a sintered funnel. The precipitate was then
Acknowledgments

ACCEPTED MANUSCRIPT
6
Tetrahedron
A. G.; Schulz, T.; Torborg, C.; Spannenberg, A.; Neumann, H.;
SP thanks CSIR New Delhi for the award of fellowship and
Beller, M. Angew. Chem.Int. Ed. 2009, 48, 7595-7599.
9. Traditionally nitroarenes are prepared by electrophilic substitution
of electron rich arenes; for reference, see: (a) Shiri, M.; Zolfigol,
M. A.; Kruger, H. G.; Tanbakouchian, Z. Tetrahedron 2010, 66,
9077-9106; (b) Olah, G. A.; Malhotra, R.; Narang, S. C. Nitration:
Methods and Mechanisms; VCH: Weinheim, 1989.
10. (a) Saito, S.; Koizumi, Y. Tetrahedron Lett. 2005, 46, 4715-4717;
(b) LaBeaume, P.; Placzek, M.; Daniels, M.; Kendrick, I.; Ng, P.;
McNeel, M.; Afroze, R.; Alexander, A.; Thomas, R.; Kallmerten,
A. E.; Jones, G. B. Tetrahedron Lett. 2010, 51, 1906-1909; (c)
Fors, B. P.; Buchwald, S. L. J. Am. Chem. Soc. 2009, 131, 12898-
12899; (d) Amal Joseph, P. J.; Priyadarshini, S.; Kantam, M. L.;
Maheswaran, H. Tetrahedron Lett. 2012, 53, 1511-1513; (e) Fors,
B. P.; Buchwald, S. L. J. Am. Chem. Soc. 2009, 131, 12898-
12899.
PJAJ thank UGC, India for the award of fellowship.
Supplementary data
XRD, XPS, FT-IR and UV DRS spectra of MOFs as well as
characterization data and copies of H and 13C NMR spectra of
1
all the compounds are provided in supplementary material.
References and notes
1. (a) Tyman, J. H. P. Synthetic and Natural Phenols, Elsevier, New
York, 1996; (b) Rapport, Z. The Chemistry of Phenols, Wiley-
VCH, Weinheim, 2003; (c) Weber, M.; Weber, M.; Kleine-
Boymann, M. In Ullmann’s Encyclopedia of Industrial Chemistry,
7th ed., Elvers, B.; Hawkins, S.; Schulz, G., Eds.; Wiley,
Weinheim, 2004; (d) Parry, R.; Nishinob, S.; Spain, J. Nat. Prod.
Rep. 2011, 28, 152-167; (e) Li, H.; Huang, H.; Zhang, X.; Luo, X.;
Lin, L.; Jiang, H.; Ding, J.; Chen, K.; Liu, H. Acta Pharmacol. Sin
2008, 12, 1529-1538; (f) Muller, W. E. The Benzodiazepine
Receptor, Cambridge University Press: New York, 1988; (g)
Belciug, M.; Ananthanarayanan, V. S. J. Med. Chem. 1994, 37,
4392-4399; (h) Zollinger, H. Color Chemistry; Wiley-VCH: New
York, 1987. p 161; (i) Agrawal, J. P. Prop. Explos. Pyrotech. 30
2005, 5, 316-328; (j) Fan, F. -R. F.; Yao, Y.; Cai, L.; Cheng, L.;
Tour, J. M.; Bard, A. J. J. Am. Chem. Soc. 2004, 126, 4035-4042.
2. (a) Ley, S. V.; Thomas, A. W. Angew. Chem., Int. Ed. 2003, 42,
5400-5449; (b) Monnier, F.; Taillefer, M. Angew. Chem., Int. Ed.
2009, 48, 6954-6971; (c) Ono, N. The Nitro Group in Organic
Synthesis; Wiley-VCH: New York, 2001; (d) Tafesh, A. M.;
Weiguny, J. Chem. Rev. 1996, 96, 2035-2052.
11. Broxton, T. J.; Muir, D. M.; Parker, A. J. J. Org. Chem., 1975, 40,
3230-3233.
12. For reviews on application of metal organic frameworks in
catalysis; see: (a) Farrusseng, D.; Aguado, S.; Pinel, C. Angew.
Chem. Int. Ed. 2009, 48, 7502-7513; (b) Corma, A.; Garcia, H.;
Llabrési Xamena, F. X. Chem. Rev. 2010, 110, 4606-4655; (c)
Ranocchiari, M.; van Bokhoven, J. A. Phys. Chem. Chem. Phys.
2011, 13, 6388-6396; (d) Lee, J. Y.; Farha, O. K.; Roberts, J.;
Scheidt, K. A.; Nguyen, S. B. T.; Hupp, J. T. Chem. Soc. Rev.
2009, 38, 1450-1459; (e) Dhakshinamoorthy, A.; Garcia, H.
Chem. Soc. Rev. 2012, 41, 5262-5284; (f) Czaja, A. U.; Trukhanb,
N.; Muller, U. Chem. Soc. Rev. 2009, 38, 1284-1293; (g) Jiang, H.
-L.; Xu, Q. Chem. Commun. 2011, 47, 3351-3370; (h) Yoon, M.;
Srirambalaji, R.; Kim, K. Chem. Rev. 2012, 112, 1196-1231; (i)
Liu, Y.; Xuan, W.; Cui, Y. Adv. Mater. 2010, 22, 4112-4135; (j)
Ma, L.; Abney, C.; Lin, W. Chem. Soc. Rev. 2009, 38, 1248.
13. (a) Li, J. -R.; Sculley, J.; Zhou, H. -C. Chem. Rev. 2012, 112, 869-
932; (b) Li, J. -R.; Kuppler, R. J.; Zhou, H. -C. Chem. Soc. Rev.
2009, 38, 1477-1504; (c) Murray, L. J.; Dinca, M.; Long, J. R.
Chem. Soc. Rev. 2009, 38, 1294-1314; (d) Kreno, L. E.; Leong,
K.; Farha, O. K;. Allendorf, M.; Van Duyne, R. P.; Hupp, J. T.
Chem. Rev. 2012, 112, 1105-1125; (e) Horcajada, P.; Gref, R.;
Baati, T.; Allan, P. K.; Maurin, G.; Couvreur, P.; Ferey, G.;
Morris, R. E.; Serre, C. Chem. Rev. 2012, 112, 1232-1268; (f)
Ferey, G.; Mellot-Draznieks, C.; Serre, C.; Millange, F. Acc.
Chem. Res. 2005, 38, 217-225; (g) Ferey, G. Chem. Soc. Rev.
2008, 37, 191-214; (h) Farha, O. K.; Eryazici, I.; Jeong, N. C.;
Hauser, B. G.; Wilmer, C. E.; Sarjeant, A. A.; Snurr, R. Q.;
Nguyen, S. T.; Yazaydın, A. O.; Hupp, J. T. J. Am. Chem. Soc.
2012, 134, 15016-15021; (i) Wee, L. H.; Lohe, M. R.; Janssens,
N.; Kaskel, S.; Martens, J. A. J. Mater. Chem. 2012, 22, 13742-
13746; (j) Furukawa, H.; Ko, N.; Go, Y. B.; Aratani, N.; Choi, S.
B.; Choi, E.; Yazaydin, A. O.; Snurr, R. Q.; O’Keeffe, M.; Kim,
J.; Yaghi, O. M. Science, 2010, 329, 424-428.
14. (a) Dhakshinamoorthy, A.; Alvaro, M.; Garcia, H. Catal. Sci.
Technol. 2011, 1, 856-867; (b) Dhakshinamoorthy, A.; Alvaro,
M.; Garcia, H. J. Catal. 2009, 267, 1-4; (c) Xie, M. -H.; Yang, X. -
L.; Wu, C. -D. Chem. Commun. 2011, 47, 5521-5523; (d)
Dhakshinamoorthy, A.; Alvaro, M.; Garcia, H. ChemCatChem
2010, 2, 1438-1443; (e) Yu, F.; Zheng, P. -Q.; Long, Y. -X.; Ren,
Y. -P.; Kong, X. -J.; Long, L. -S.; Yuan, Y. -Z.; Huang, R. -B.;
Zheng, L. -S. Eur. J. Inorg. Chem. 2010, 4526-4531; (f) Biswas,
S.; Maes, M.; Dhakshinamoorthy, A.; Feyand, M.; De Vos, D. E.;
Garcia, H.; Stoc, N. J. Mater. Chem. 2012, 22, 10200-10209; (g)
Dhakshinamoorthy, A.; Alvaro, M.; Garcia, H. ACS Catal. 2011,
1, 48-53; (h) Marx, S.; Kleist, W.; Baiker, A. J. Catal. 2011, 281,
76-87; (i) Hwang, Y. K.; Hong, D. -Y.; Chang, J. -S.; Seo, H.;
Yoon, M.; Kim, J.; Jhung, S. H.; Serre, C.; Ferey, G. Appl. Catal.
A 2009, 358, 249-253.
3. (a) Ballini, R.; Petrini, M. Tetrahedron 2004, 60, 1017-1047; (b)
Frantz, D. E.; Weaver, D. G.; Carey, J. P.; Kress, M. H.; Dolling,
U. H. Org. Lett. 2002, 4, 4717-4718; (c) Larsson, P. -F.; Correa,
A.; Carril, M.; Norrby, P. -O.; Bolm, C. Angew. Chem., Int. Ed.
2009, 48, 5691-5693.
4. (a) Trost, B. M. Science 1991, 254, 1471-1472; b) Trost, B. M.
Angew. Chem., Int. Ed. Engl. 1995, 34, 259-281.
5. (a) Fyfe, C. A. In The Chemistry of the Hydroxyl Group, Patai, S.
Ed.; Wiley-Interscience, New York, 1971, vol. 1, pp. 83–127; (b)
George, T.; Mabon, R.; Sweeney, G.; Sweeney, J. B.; Tavassoli,
A. J. J. Chem. Soc. Perkin Trans. 1 2000, 2529-2574; (c) Hanson,
P.; Jones, J. R.; Taylor, A. B.; Walton, P. H.; Timms, A. W. J.
Chem. Soc. Perkin Trans. 2 2002, 1135-1150; (d) Hoarau, C.;
Pettus, T. R. R. Synlett 2003, 127-137; (e) Wu, Z.; Glaser, R. J.
Am. Chem. Soc. 2004, 126, 10632-10639; (f) Xu, J.; Wang, X.;
Shao, C.; Su, D.; Cheng, G.; Hu, Y. Org. Lett. 2010, 9, 1964-1967.
6. For selectivity towards symmetrical diarylethers in hydroxylation,
see reference: Tlili, A.; Monnier, F.; Taillefer, M. Chem. Eur. J.
2010, 16, 12299-12302
7. (a) Tlili, A.; Xia, N.; Monnier, F.; Taillefer, M. Angew. Chem., Int.
Ed. 2009, 48, 8725-8728; (b) Zhao, D.; Wu, N.; Zhang, S.; Xi, P.;
Su, X.; Lan, J.; You, J. Angew. Chem., Int. Ed. 2009, 48, 8729-
8732; (c) Maszurer, S.; Liu, W.; Zhang, X.; Jiang, Y.; Ma, D.
Synlett 2010, 976-978; (d) Yang, D.; Fu, H. Chem. Eur. J. 2010,
16, 2366-2370; (e) Jing, L.; Wei, J.; Zhou, L.; Huang, Z.; Li, Z.;
Zhou, X. Chem. Commun. 2010, 46, 4767-4769; (f) Xu, H. -J.;
Liang, Y. -F.; Cai, Z. -Y.; Qi, H. -X.; Yang, C. -Y.; Feng, Y. -S. J.
Org. Chem. 2011, 76, 2296-2300; (g) Thakur, K. G.; Sekar, G.
Chem. Commun. 2011, 47, 6692-6694; (h) Amal Joseph, P. J.;
Priyadarshini, S.; Kantam, M. L.; Maheswaran, H. Catal. Sci.
Technol. 2011, 1, 582-585; (i) Yang, K.; Li, Z.; Wang, Z.; Yao, Z.;
Jiang, S.; Org. Lett. 2011, 13, 4340-4343; (j) Jia, J.; Jiang, C.;
Zhang, X.; Jiang, Y.; Ma, D. Tetrahedron Lett. 2011, 52, 5593-
5595; (k) Alonso, D. A.; Najera, C.; Pastor, I. M.; Yus, M. Chem.
Eur. J. 2010, 16, 5274-5284.
15. (a) Hermannsdorfer, J.; Kempe, R. Chem. Eur. J. 2011, 17, 8071-
8077; (b) Liu, H.; Li, Y.; Luque, R.; Jiang, H. Adv. Synth. Catal.
2011, 353, 3107-3113.
16. (a) Song, F.; Wang, C.; Lin, W. Chem. Commun. 2011, 47, 8256-
8258; (b) Lee, D. H.; Kim, S.; Hyun, M. Y.; Hong, J. -Y.; Huh, S.;
Kim, C.; Lee, S. J. Chem. Commun. 2012, 48, 5512-5514.
17. (a) Lu, W.; Yuan, D.; Yakovenko, A.; Zhou, H. -C. Chem.
Commun. 2011, 47, 4968-4970; (b) Shi, F. -N.; Silvan, A. R.;
Rocha, J. J. Solid State Chem. 2011,184, 2196-2203.
18. (a) Dhakshinamoorthy, A.; Alvaro, M.; Garcia, H. Chem. Eur. J.
2010, 16, 8530-8536; (b) Britt, D.; Lee, C.; Uribe-Romo, F. J.;
Furukawa, H.; Yaghi, O. M. Inorg. Chem. 2010, 49, 6387-6389.
19. (a) Dang, D.; Wu, P.; He, C.; Xie, Z.; Duan, C. J. Am. Chem. Soc.
2010, 132, 14321-14323; (b) Ladrak, T.; Smulders, S.; Roubeau,
8. (a) Anderson, K. W.; Ikawa, T.; Tundel, R. E.; Buchwald, S. L. J.
Am. Chem. Soc. 2006, 128, 10694-10695; (b) Wills, M. C. Angew.
Chem. Int. Ed. 2007, 46, 3402-3404; (c) Gallon, B. J.; Kojima, R.
W.; Kaner, R. B.; Diaconescu, P. L. Angew. Chem. Int. Ed. 2007,
46, 7251-7254; (d) Chen, G.; Chan, A. S. C.; Kuong, F. Y.
Tetrahedron Lett. 2007, 48, 473-476; (e) Schulz, T.; Torborg, C.;
Schaffner, B.; Huang, J.; Zapf, A.; Kadyrou, R.; Borner, A.;
Beller, M. Angew. Chem., Int. Ed. 2009, 48, 918-921; (f) Sergeev,

ACCEPTED MANUSCRIPT
7
O.; Teat, S. J.; Gamez, P.; Reedijk, J. Eur. J. Inorg. Chem. 2010,
3804-3812; (c) Gu, J. -M.; Kim, W. -S.; Huh, S. Dalton Trans.
2011, 40, 10826-10829; (d) Schlichte, K.; Kratzke, T.; Kaskel, S.
Microporous Mesoporous Mater. 2004, 73, 81-88.
20. (a) Deng, M.; Ling, Y.; Xia, B.; Chen, Z.; Zhou, Y.; Liu, X.; Yue,
B.; He, H. Chem. Eur. J. 2011, 17, 10323-10328; (b) Phan, N. T.
S.; Le, K. K. A.; Phan, T. D. Appl. Catal. A 2010, 382, 246-253;
(c) Roberts, J. M.; Fini, B. M.; Sarjeant, A. A.; Farha, O. K.;
Hupp, J. T.; Scheidt, K. A.; J. Am. Chem. Soc. 2012, 134, 3334-
3337.
21. (a) Llabrési Xamena, F. X.; Cirujano, F. G.; Corma, A.
Microporous Mesoporous Mater. 2012, 157,112-117; (b) Hong, D.
-Y.; Hwang, Y. K.; Serre, C.; Ferey, G.; Chang, J. -S. Adv. Funct.
Mater. 2009, 19, 1537-1552; (c) Hwang, Y. K.; Hong, D. -Y.;
Chang, J. -S.; Jhung, S. H.; Seo, Y. -K.; Kim, J.; Vimont, A.;
Daturi, M.; Serre, C.; Ferey, G. Angew. Chem. Int. Ed. 2008, 47,
4144-4148.
22. (a) Sachse, A.; Ameloot, R.; Coq, B.; Fajula, F.; Coasne, B.; De
Vos, D.; Galarneau, A. Chem. Commun. 2012, 48, 4749-4751; (b)
Pérez-Mayoral, E.; Čejka, J. ChemCatChem 2011, 3, 157-159.
23. (a) Dhakshinamoorthy, A.; Alvaro, M.; Garcia, H. Adv. Synth.
Catal. 2010, 352, 3022-3030; (b) Dhakshinamoorthy, A.; Alvaro,
M.; Garcia, H. Appl. Catal. A 2010, 378, 19-25; (c) Luz, I.;
Llabrési Xamena, F. X.; Corma, A. J. Catal., 2010, 276, 134-140;
(d) Huang, Y.; Lin, Z.; Cao, R. Chem. Eur. J. 2011, 17, 12706-
12712; (e) Vitorino, M. J.; Devic, T.; Tromp, M.; Ferey, G.;
Visseaux, M. Macromol. Chem. Phys. 2009, 210, 1923-932; (f)
Pathan, N. B.; Rahatgaonkar, A. M.; Chorghade, M. S. Catal.
Commun. 2011, 12, 1170-1176; (g) Ma, L.; Wanderley, M. M.;
Lin, W. ACS Catal. 2011, 1, 691-697; (h) Lalonde, M. B.; Farha,
O. K.; Scheidt, K. A.; Hupp, J. T. ACS Catal. 2012, 2, 1550-1554;
(i) Arnanz, A.; Pintado-Sierra, M.; Corma, A.; Iglesias, M.;
Sánchez, F. Adv. Synth. Catal. 2012, 354, 1347-1355; (j) Ma, L.;
Falkowski, J. M.; Abney, C.; Lin, W. Nature Chem. 2010, 2, 838-
846; (k) Dhakshinamoorthy, A.; Alvaro, M.; Garcia, H. Chem.
Commun. 2012, 48, 11275-11288.
24. For examples of MOFs as catalyst in coupling reactions, see: (a)
Llabrési Xamena, F. X.; Abad, A.; Corma, A.; Garcia, H. J. Catal.
2007, 250, 294-298; (b) Wang, M.; Yuan, B.; Ma, T.; Jiang, H.;
Li, Y. RSC Adv. 2012, 2, 5528-5530; (c) Dang, T. T.; Zhu, Y.;
Ghosh, S. C.; Chen, A.; Chai, C. L. L.; Seayad, A. M. Chem.
Commun. 2012, 48, 1805-1807; (d) Huang, Y.; Gao, S.; Liu, T.;
Lü, J.; Lin, X.; Li, H.; Cao, R. ChemPlusChem 2012, 77, 106-
112; (e) Huang, Y.; Zheng, Z.; Liu, T.; Lü, J.; Lin, Z.; Li, H.; Cao,
R. Catal. Commun. 2011, 14, 27-31; (f) Ding, S. -Y.; Gao, J.;
Wang, Q.; Zhang, Y.; Song, W.- G.; Su, C. -Y.; Wang, W. J. Am.
Chem. Soc. 2011, 133, 19816-19822; (g) Gao, S.; Zhao, N.; Shu,
M.; Che, S. Appl. Catal. A 2010, 388, 196-201.
25. For a rare example of application of Cu MOFs in catalytic C-O
bond formation of aryl halides, see reference 23 b
26. Wang, W.; Zhan, Y.; Wang, G. Chem. Commun. 2001, 727-728.
27. Dhakshinamoorthy, A.; Alvaro, M.; Concepcion, P.; Garcia, H.
Cat. Comm. 2011, 12, 1018-1023.
28. Kida, T.; Oka, T.; Nagano, M. J. Am. Ceram. Soc. 2007, 90, 107-
110.
29. The studies with filtrate were not performed, due to the difficulty
encountered in recovery of the biphasic layer without the addition
of additional solvents. CuO was not soluble in reaction solution.
30. Significant amount of CuO was formed initially, as inferred from
the analysis of recovered catalyst (after 3 h from begin of
reaction).
31. (a) Hartmann, M.; Kunz, S.; Himsl, D.; Tangermann, O. Langmuir
2008, 24, 8634-8642; (b) Chui, S. S. -Y.; Lo, S. M. -F.; Charmant,
J. P. H.; Orpen, A. G.; Williams, I. D. Science 1999, 283, 1148-
1150.
32. Carson, C. G.; Hardcastle, K.; Schwartz, J.; Liu, X.; Hoffmann,
C.; Gerhardt, R. A.; Tannenbaum, R. Eur. J. Inorg. Chem. 2009,
2338-2343.
33. Tabares, L. C.; Navarro, J. A. R.; Salas, J. M. J. Am. Chem. Soc.
2001, 123, 383-387.
34. Masciocchi, N.; Bruni, S.; Cariati, E.; Cariati, F.; Galli, S.; Sironi,
A. Inorg. Chem. 2001, 40, 5897-5905.

ACCEPTED MANUSCRIPT
Copper MOF: Scope and limitation in catalytic
hydroxylation and nitration of aryl halides
S. Priyadarshini, P. J. Amal Joseph, M. Lakshmi Kantam, and B. Sreedhar
Inorganic and Physical Chemistry Division, CSIR-Indian Institute of Chemical Technology,
Hyderabad – 500607, India
Fax: +91-40-27160921; E-mail: mlakshmi@iict.res.in
Table of contents
ChemDraw image ------------------------------------------------------------------------ S2
XRD patterns ------------------------------------------------------------------------ S3-S5
XPS spectra --------------------------------------------------------------------------- S6-S8
FT IR spectrum------------------------------------------------------------------------S9-S10
UV DRS spectrum------------------------------------------------------------------------S10
Analytical data --------------------------------------------------------------------- S11-S14
References ------------------------------------------------------------------------------ S-15
1H and 13C NMR spectra ----------------------------------------------------------- S16-S40
S1

ACCEPTED MANUSCRIPT
ChemDraw image
Fig.S1. A simplified pictorial representation of Dicopper(II) tetracarboxylate building block
of Cu3(btc)2 framework
S2

ACCEPTED MANUSCRIPT
XRD pattern of Cu3(btc)2.3H2O
XRD pattern of Cu(bdc).dmf
S3

ACCEPTED MANUSCRIPT
XRD pattern of Cu(pymo).2.25H2O
XRD pattern of recovered Cu3(btc)2.3H2O (nitration)
S4

ACCEPTED MANUSCRIPT
XRD pattern of used catalyst (hydroxylation) [Cu3(btc)2 is transformed into CuO]
XRD pattern of recovered catalyst (hydroxylation) [Cu(im)2 is transformed into CuO]
S5

ACCEPTED MANUSCRIPT
XPS spectra of Cu3(btc)2.3H2O
S6

ACCEPTED MANUSCRIPT
XPS spectra of recovered Cu3(btc)2.3H2O (nitration)
S7

ACCEPTED MANUSCRIPT
XPS spectra of recovered catalyst in hydroxylation (Cu3(btc)2 is transformed into CuO)
S8

ACCEPTED MANUSCRIPT
FT IR spectrum of Cu3(btc)2.H2O
FT IR spectrum of recovered Cu3(btc)2.H2O (nitration)
S9

ACCEPTED MANUSCRIPT
FT IR spectrum of recovered Cu3(btc)2.H2O (hydroxylation)
UV DRS spectrum of Cu3(btc)2
S10

ACCEPTED MANUSCRIPT
Analytical Data
Phenol (Table 2, entry 1)[1]; 1H NMR (300 MHz, CDCl3): δ = 7.22-7.14 (m, 2H), 6.87 (t, J =
7.4 Hz, 1H), 6.77 (d, J = 7.6 Hz, 2H), 5.95 (brs, 1H); 13C NMR (75 MHz, CDCl3): δ =
155.36, 129.65, 120.77, 115.32.
4-methoxyphenol (Table 2, entry 2 & 20)[1]; 1H NMR (300 MHz, CDCl3): δ = 6.73-6.67 (m,
13
4H), 5.57 (brs, 1H), 3.73 (s, 3H); C NMR (75 MHz, CDCl3): δ = 153.27, 149.43, 116.10,
114.95, 55.82.
p-cresol (Table 2, entry 3)[1]; 1H NMR (300 MHz, CDCl3): δ = 6.97 (d, J = 8.3 Hz, 2H), 6.65
(d, J = 8.3 Hz, 2H), 4.90 (s, 1H), 2.26 (s, 3H); 13C NMR (75 MHz, CDCl3): δ = 153.04,
130.01, 129.89, 115.13, 20.36.
4-(tert-butyl)phenol (Table 2, entry 4)[2]; 1H NMR (300 MHz, CDCl3): δ =7.22-7.16 (m, 2
H), 6.74-6.68 (m, 2H), 5.44 (brs, 1H), 1.28 (s, 9H); 13C NMR (75 MHz, CDCl3): δ = 153.17,
143.45, 126.39, 114.73, 34.05, 31.52.
4-(methylthio)phenol (Table 2, entry 5)[3]; 1H NMR (300 MHz, CDCl3): δ = 7.21 (d, J = 9.1
Hz, 2H), 6.78 (d, J = 9.1 Hz, 2H), 5.30 (brs, 1H), 2.44 (s, 3H); 13C NMR (75 MHz, CDCl3): δ
= 154.09, 130.93, 130.34, 116.04, 18.03.
4-chlorophenol (Table 2, entry 6)[1]; 1H NMR (300 MHz, CDCl3): 7.16-7.10 (m, 2H), 6.74-
13
6.67 (m, 2H), 6.33 (brs, 1H); δ = C NMR (75 MHz, CDCl3): δ = 154.24, 129.48, 125.56,
116.66.
S11

ACCEPTED MANUSCRIPT
4-(1H-pyrrol-1-yl)phenol (Table 2, entry 7)[4]; 1H NMR (300 MHz, CDCl3): δ = 7.29-7.23
(m, 2H), 6.99 (t, J = 2.3 Hz, 2H), 6.91-6.85 (m, 2H), 6.32 (t, J = 2.3 Hz, 2H), 5.12 (brs, 1H);
13C NMR (75 MHz, CDCl3): δ = 153.52, 134.57, 122.37, 119.68, 116.05, 109.80.
naphthalen-2-ol (Table 2, entry 8)[1]; 1H NMR (300 MHz, CDCl3): δ = 7.71 (dd, J = 8.3, 3.0
Hz, 2H), 7.62 (d, J = 8.3 Hz, 1H), 7.41-7.34 (m, 1H), 7.30-7.26 (m, 1H), 7.09-7.07 (m, 1H),
7.04 (dd, J = 8.3, 3.0 Hz, 1H), 4.83 (s, 1H); 13C NMR (75 MHz, CDCl3): δ = 153.19, 134. 51,
129.83, 128.89, 127.72, 126.50, 126.33, 123.61, 117.68, 109.48.
3-(benzyloxy)phenol (Table 2, entry 9)[5]; 1H NMR (300 MHz, CDCl3): δ = 7.43-7.28 (m,
5H), 7.11 (t, J = 8.3 Hz, 1H), 6.58-6.52 (m, 1H), 6.48-6.45 (m, 1H), 6.44-6.39 (m, 1H), 5.48
(brs, 1H), 4.99 (s, 2H); 13C NMR (75 MHz, CDCl3): δ = 160.06, 156.71, 136.83, 130.12,
128.53, 127.93, 127.45, 108.14, 107.28, 102.52, 70.03.
naphthalen-1-ol (Table 2, entry 10)[5]; 1H NMR (300 MHz, CDCl3): δ = 8.16-8.09 (m, 1H),
7.78-7.72 (m, 1H), 7.46-7.41 (m, 2H), 7.37 (d, J = 8.3 Hz, 1H), 7.22 (t, J = 7.8 Hz, 1H), 6.70
(d, J = 7.4 Hz, 1H), 5.28 (brs, 1H); 13C NMR (75 MHz, CDCl3): δ = 151.25, 134.72, 127.65,
126.40, 125.80, 125.24, 124.33, 121.45, 120.69, 108.67.
pyrocatechol (Table 2, entry 11)[6]; 1H NMR (300 MHz, CDCl3): δ = 6.84-6.71 (m, 4H), 5.16
(s, 2H); 13C NMR (75 MHz, CDCl3): δ = 143.12, 121.14, 115.52.
2,6-dimethoxyphenol (Table 2, entry 12)[7]; 1H NMR (300 MHz, CDCl3): δ = 6.77 (t, J = 8.3
Hz, 1H), 6.55 (d, J = 8.3 Hz, 2H), 5.56 (brs, 1H), 3.87 (s, 6H); 13C NMR (75 MHz, CDCl3): δ
= 147.10, 134.68, 118.92, 104.75, 56.09.
4-nitrophenol (Table 2, entry 13, 16 & 21)[1]; 1H NMR (300 MHz, CDCl3): δ = 8.21-8.14 (m,
2H), 6.97-6.91 (m, 2H), 6.59 (brs, 1H); 13C NMR (75 MHz, CDCl3): δ = 162.87, 139.00,
124.84, 114.60.
S12

ACCEPTED MANUSCRIPT
1-(4-hydroxyphenyl)ethanone (Table 2, entry 14, 15 & 22)[1]; 1H NMR (300 MHz, CDCl3):
δ = 9.76 (brs, 1H), 7.77 (d, J = 8.7 Hz, 2H), 6.80 (d, J = 8.7 Hz, 2H), 2.48 (s, 3H); 13C NMR
(75 MHz, CDCl3): δ = 198.86, 161.62, 131.22, 129.35, 115.56, 26.21.
quinolin-6-ol (Table 2, entry 17)[2]; 1H NMR (500 MHz, DMSO-d6): δ = 9.97 (s, 1H), 8.69
(s, 1H), 8.07 (d, J = 7.8 Hz, 1H), 7.89 (d, J = 8.9 Hz, 1H), 7.37-7.29 (m, 2H), 7.15 (s, 1H);
13C NMR (75 MHz, DMO-d6): δ = 153.77, 145.07, 141.34, 132.23, 128.47, 127.55, 120.18,
119.37, 106.53.
quinolin-3-ol (Table 2, entry 18)[2]; 1H NMR (300 MHz, DMSO-d6): δ = 9.91 (s, 1H), 8.55
13
(d, J = 2.6 Hz, 1H), 7.92-7.86 (m, 1H), 7.67-7.61 (m, 1H), 7.44-7.37 (m, 3H); C NMR (75
MHz, CDCl3): δ = 150.08, 142.99, 141.62, 128.29, 127.59, 125.70, 125.37, 124.89, 115.02.
3-(pyrimidin-4-yl)phenol (Table 2, entry 19)[8]; 1H NMR (300 MHz, CDCl3+DMSO-d6): δ =
9.30-9.19 (m, 2H), 8.75 (d, J = 5.3 Hz, 1H), 7.72 (d, J = 5.5 Hz, 1H), 7.61(s, 1H), 7.57-7.51
(m, 1H), 7.33 (t, J = 7.8 Hz, 1H), 7.03-6.98 (m, 1H); 13C NMR (75 MHz, CDCl3+DMSO-d6):
δ = 163.34, 158.28, 157.52, 156.82, 137.14, 129.48, 117.98, 117.56, 116.61, 113.60.
1
methyl(4-nitrophenyl)sulfane (Table 4, entry 1)[9]; H NMR (300 MHz, CDCl3): δ = 8.12
13
(d, J = 9.1 Hz, 2H), 7.27 (d, J = 9.1 Hz, 2H), 2.55 (s, 3H); C NMR (75 MHz, CDCl3): δ =
148.10, 144.62, 124.87, 123.80, 14.75.
2-nitronaphthalene (Table 4, entry 2)[10]; 1H NMR (300 MHz, CDCl3): 1H NMR (300 MHz,
CDCl3): δ = 8.78 (s, 1H), 8.28-8.19 (m, 1H), 8.05-7.98 (m, 1H), 7.97-7.87 (m, 2H), 7.71-7.57
13
(m, 2H); C NMR (75 MHz, CDCl3): δ = 145.42, 135.68, 131.84, 129.89, 129.60, 129.37,
127.89, 127.80, 124.46, 119.19.
1
1
1-(4-nitrophenyl)-1H-pyrrole (Table 4, entry 3)[11]; H NMR (500 MHz, CDCl3): H NMR
(300 MHz, CDCl3): δ = 8.31 (d, J = 8.3 Hz, 2H), 7.51 (d, J = 9.3 Hz, 2H), 7.13-7.10 (m, 2H),
S13

ACCEPTED MANUSCRIPT
6.39-6.36 (m, 2H); 13C NMR (75 MHz, CDCl3): δ = 145.25, 144.82, 125.58, 119.41, 119.01,
112.67.
1-(benzyloxy)-3-nitrobenzene (Table 4, entry 4)[11]; 1H NMR (300 MHz, CDCl3): δ = 7.83-
7.75 (m, 2H), 7.43-7.28 (m, 6H), 7.26-7.22 (m, 1H), 5.10 (s, 2H); 13C NMR (75 MHz,
CDCl3): δ = 159.18, 149.20, 135.70, 129.93, 128.73, 128.38, 127.53, 121.86, 115.94, 109.21,
70.57.
1-methoxy-3-nitrobenzene (Table 4, entry 5)[12]; 1H NMR (300 MHz, CDCl3): δ = 7.80 (d, J
= 7.4 Hz, 1H), 7.69 (s, 1H), 7.40 (t, J = 8.1 Hz, 1H), 7.18 (d, J = 8.3 Hz, 1H), 3.89 (s, 3H);
13C NMR (75 MHz, CDCl3): δ = 160.12, 149.26, 129.87, 121.23, 115.73, 108.05, 55.74.
1,3-dinitrobenzene (Table 4, entry 6)13]; 1H NMR (300 MHz, CDCl3): δ = 8.99 (s, 1H), 8.65-
8.58 (m, 2H), 7.91 (t, J = 8.2 Hz, 1H); 13C NMR (75 MHz, CDCl3): δ = 148.21, 130.69,
128.75, 118.74.
1
(4-nitrophenyl)(phenyl)methanone (Table 4, entry 7)[12]; H NMR (500 MHz, CDCl3): δ =
8.33 (d, J = 8.0 Hz, 2H), 7.92 (d, J = 8.0 Hz, 2H), 7.78 (d, J = 7.0 Hz, 2H), 7.63 (t, J = 7.5
13
Hz, 1H), 7.51 (t, J = 7.5 Hz, 2H); C NMR (75 MHz, CDCl3): δ = 194.57, 149.97, 142.94,
136.42, 133.50, 130.78, 130.20, 128.77, 123.63.
6-nitroquinoline (Table 4, entry 8)[12]; 1H NMR (300 MHz, CDCl3): δ = 9.05 (d, J = 4.0 Hz,
1H), 8.75 (d, J = 3.0 Hz, 1H), 8.45 (dd, J = 9.5, 2.5 Hz, 1H), 8.31 (d, J = 8.0 Hz, 1H), 8.21 (d,
13
J = 10.0 Hz, 1H), 7.53 (dd, J = 4.0, 4.0 Hz, 1H); C NMR (75 MHz, CDCl3): δ = 153.75,
150.10, 145.42, 137.77, 131.31, 126.94, 124.54, 122.81, 122.80.
S14

ACCEPTED MANUSCRIPT
References
[1] Tlili, A.; Xia, N.; Monnier, F.; Taillefer, M. Angew. Chem., Int. Ed. 2009, 48, 8725-
8728.
[2] Anderson, K. W.; Ikawa, T.; Tundel, R. E.; Buchwald, S. L. J. Am. Chem. Soc. 2006,
128, 10694-10695.
[3] Samant, B. S.; Sukhthankar, M. G. Bioorg. Med. Chem. Lett. 2011, 21, 1015-1018.
[4] Das, B.; Shinde, D. B.; Kanth, B. S.; Kumar, J. N. Syn. Comm. 2012, 42, 548-553.
[5] Balamurugan, S.; Kannan, P.; Yadupati, K.; Roy, A. J. Mol. Struct. 2011, 1001, 118-
124.
[6] Thakur, K. G.; Sekar, G. Chem. Commun. 2011, 47, 6692-6694.
[7] Martin, T. S.; Kikuzaki, H.; Hisamoto, M.; Nakatani, N. JAOCS 2000, 77, 667-673.
[8] Schkurko, Chem. Abstr. 1979 , 90, 121532.
[9] Luo, F.; Pan, C.; Li, L.; Chen, F.; Cheng, J. Chem. Commun. 2011, 47, 5304-5306.
[10] Fors, B. P.; Buchwald, S. L. J. Am. Chem. Soc. 2009, 131, 12898-12899.
[11] Amal Joseph, P. J.; priyadarshini, S.; Kantam, M. L.; Maheswaran, H. Tetrahedron
Lett. 2012, 53, 1511-1513.
[12] Yang, H.; Li, Y.; Jiang, M.; Wang, J.; Fu, H. Chem. Eur. J. 2011, 17, 5652-5660.
[13] Domalewski, W.; Stefaniak, L.; Webb, G. A. J. Mol. Struct. 1993, 295, 19-23.
S15

ACCEPTED MANUSCRIPT
1H & 13C NMR Spectra
Phenol (Table 2, entry 1)
S16

ACCEPTED MANUSCRIPT
4-methoxyphenol (Table 2, entry 2 & 20)
S17

ACCEPTED MANUSCRIPT
p-cresol (Table 2, entry 3)
S18

ACCEPTED MANUSCRIPT
4-(tert-butyl)phenol (Table 2, entry 4)
S19

ACCEPTED MANUSCRIPT
4-(methylthio)phenol (Table 2, entry 5)
S20

ACCEPTED MANUSCRIPT
4-chlorophenol (Table 2, entry 6)
S21