Synthesis and Characterization Chapter 2
57
CHAPTER 2 Synthesis of Octa-O-methoxy Resorcin[4]arene and Its
Derivatives via Conventional and Microwave Assisted
Methods Followed by Spectroscopic Characterization
Synthesis and Characterization Chapter 2
58
Resume
Octa-O-methoxy resorcin[4]arene and its various azo-derivatives have
synthesized by conventional as well as by simple, rapid and environment-friendly
method using microwave irradiation technique. Octa-O-methoxy resorcin[4]arene
has been further converted to its tetraacetate and tetrahydrazide derivatives. Novel
octa-O-methoxy resorcin[4]arene Amberlite XAD-4 polymeric chelating resin has
also been synthesized by covalently linked diazotized Amberlite XAD-4 with octa-O-
methoxy resorcin[4]arene. All of the synthesized compounds have been checked for
their purity by TLC and characterized by elemental analysis, FT-IR, 1H NMR,13C NMR
and ESI-MS.
Synthesis and Characterization Chapter 2
59
TABLE OF CONTENTS
1. Introduction 60
2. Experimental 62
3. Synthesis 63
3.1 Synthesis of octa-O-methoxy resorcin[4]arene via conventional and
microwave assisted methods
3.1.1 Conventional method
3.1.2 Microwave irradiation method
63
63
63
3.2 Synthesis of octa-O-methoxy resorcin[4]arene tetrahydrazide via
conventional method
3.2.1 Octa-O-methoxy resorcin[4]arene acetate derivative
3.2.2 Octa-O-methoxy resorcin[4]arene tetrahydrazide derivative
64
64
3.3 Synthesis of octa-O-methoxy resorcin[4]arene Amberlite XAD-4 polymeric
chelating resins through azo(-N=N-) linkage 65
3.4 Synthesis of azo-octa-O-methoxy resorcin[4]arene dyes
3.4.1 General procedure for the synthesis by conventional method
3.4.2 Microwave irradiation method for the synthesis
66
66
67
4. Results and discussion 71
4.1 Synthesis and spectroscopic characterization
4.1.1 Conventional and microwave assisted synthesis of octa-O-methoxy
resorcin[4]arene
4.1.2 Synthesis of octa-O-methoxy resorcin[4]arene tetrahydrazide
derivative
4.1.3 Octa-O-methoxy resorcin[4]arene Amberlite XAD-4 polymeric
chelating resin
4.1.4 Azo dyes of octa-O-methoxy resorcin[4]arene
4.2 Determination of crystal structure of octa-O-methoxy resorcin[4]arene
71
71
72
73
74
75
Conclusion 75
References 89
Synthesis and Characterization Chapter 2
60
1. Introduction
The impact of supramolecular research is in design and synthesis of molecules
that respond to a particular analyte [1]. Synthetic molecular recognition modeling in
supramolecular chemistry has yielded a wide variety of cavity-containing host
molecules, capable of binding a range of guest molecules [2, 3].
Calix[4]resorcinarenes [4, 5], the most stable conformer having a bowl shaped
molecular cavity have attracted great interest in recent years due to their versatile
complexing properties, conformational flexibility, a great variety of ways for their
further functionalization and an easy synthetic and commercial availability.
There are many applications of calix[4]resorcinarenes and their
functionalized derivatives, like as a modified carbon-fiber electrode [6], HPLC
stationary phase [7], light-grated artificial ion channels [8], Molecular glass resists
[9-11], imaging material for organic electronics [12], NMR solvating agents [13],
PVC supported liquid membrane electrodes [14], multifunctional antiradical and
antioxidant agents [15], photoresist material [16] have been reported.
There has been remarkable progress in the preparation of
calix[4]resorcinarene by using gentle procedures while effectively embracing the
principles of green chemistry. Lanthanide(III) nitrobenzenesulfonates and p-
toluenesulfonate complexes of lanthanide(III), iron(III), and copper(II) have been
used as catalysts for the formation of calix[4]resorcinarene [17]. Solvent-free
synthesis of arylcalix[4]resorcinarene and C-methylcalix[4]resorcinarene by simply
grinding together resorcinol with aldehydes in the presence of a catalytic amount of
p-toluenesulfonic acid have been reported [18, 19]. Recently, an efficient solvent-
Synthesis and Characterization Chapter 2
61
free synthesis of novel calix[4]resorcinarene derivative using tungstate sulfuric acid
has been reported [20]. The synthesis of calix[4]resorcinarene based on fennel oil
has also been reported in literature [21].
The challenges in chemistry to develop the practical methods, reaction
media, conditions and/or the use of materials based on the idea of green chemistry
is one of the important issues in the scientific community [22]. These green methods
provide simple, fast, high-yielding, and non-polluting synthetic routes of
resorcinarene and these efficient processes should be potentially applicable to the
preparation of other calixarene systems as well. In last decades, microwave
irradiation technique has played an important role as a very effective and non
polluting method for activating reactions because it takes less time with improved
yield, uses milder reaction conditions and environmental friendly [23, 24].
Calix[4]resorcinarenes form a relatively shallow conical cavity that can be
extended by suitable substitution and further functionalization. Interest in
calix[4]resorcinarenes has grown rapidly also because of the numerous
derivatization that can be created through comparatively simple synthetic
procedures by substitution at their upper rim, methylene bridges and hydroxyl
group at the extra annular position to alter their properties and applications. Azo
compounds are used as an important class of dyes due to their multipurpose
applications in various fields such as the dyeing of textile fibers, the coloring of
different materials, biological studies and advanced applications in organic
synthesis [25-28].
Synthesis and Characterization Chapter 2
62
Herein, we report synthesis of octa-O-methoxy resorcin[4]arene using 1,3
dimethoxy benzene and p-hydroxy benzaldehyde via acid catalyzed condensation
reaction by conventional as well as microwave irradiation method. Likewise its two
new azo derivatives have also been prepared. Octa-O-methoxy resorcin[4]arene has
been further converted to its tetraacetate and tetrahydrazide derivatives. Octa-O-
methoxy resorcin[4]arene Amberlite XAD-4 polymeric chelating resin has been
synthesized by covalently linking diazotized Amberlite XAD-4 with octa-O-methoxy
resorcin[4]arene.
2. Experimental
All reagents and solvents of analytical grade, purchased from Sigma-Aldrich,
Fluka, and CDH were used without further purification. All aqueous solutions were
prepared from Millipore water (resistivity, 18 ΩX; Millipore Systems). Amberlite
XAD-4 with surface area 750 m2 g−1, pore diameter 50 Å and bead size 20–50 mesh
was procured from Fluka. Microwave synthesis work was carried out using a CEM
Discover Microwave Synthesizer. Julabo F 25 bath was used for the reactions carried
out at a lower temperature. TLC plates (F-2009) fluorescence active were obtained
from Merck. The melting points (uncorrected) were obtained from a VEEGO (Model;
VMP-DS) melting point apparatus. Elemental analysis was done on Elementar vario
micro cube. FT-IR spectra were recorded on Bruker tensor 27 infrared spectrometer
with samples prepared as KBr pellets. 1H NMR and 13C NMR spectra were recorded
on a Bruker-ARX 500 instrument, using tetramethylsilane (TMS) as internal
standard. Mass Spectra (ESI-MS) were recorded on MICROMASS QUATTRO II triple
quadruple mass spectrometer (3.5 KV, 40 V).
Synthesis and Characterization Chapter 2
63
3. Synthesis
3.1 Synthesis of octa-O-methoxy resorcin[4]arene via conventional and
microwave assisted methods ( Scheme 1)
3.1.1 Conventional method
Basic platform octa-O-methoxy resorcin[4]arene (1) was synthesized by the
acid catalyzed condensation reaction of 1,3 dimethoxy benzene and p-hydroxy
benzaldehyde. Aqueous hydrochloric acid (9.0M, 0.8 mL) was added dropwise to a
stirring solution of 1,3 dimethoxy benzene (0.528 g, 3.82 mmol) and p-
hydroxybenzaldehyde (0.46 g, 3.82 mmol) in ethanol (65 mL) the reaction mixture
was refluxed with constant stirring for 12 hours. The mixture was allowed to cool at
room temperature and then filtered to yield the crude purple product, which was
further washed with cold methanol and recrystallized in DMF- methanol mixture
[29].
3.1.2 Microwave irradiation method
To a mixture of 1, 3 dimethoxy benzene (0.528 g, 3.82 mmol) and p-hydroxy
benzaldehyde (0.46 g, 3.82 mmol) in ethanol (65 mL), aqueous hydrochloric acid
(9.0M, 0.8 mL) was added drop wise. The reaction mixture was subjected to
microwave irradiation for approximately 10-12 minutes with a break of one minute
after the regular interval of 2 minutes, for the purpose of stirring. After which the
reaction mixture was filtered off to get the crude mixture as a purple powder.
Octa-O-methoxy resorcin[4]arene (1) possessed significant importance of
binding analyte under different conditions. To improve their binding ability, they
can be functionalized with some chelating/chromogenic groups. With this in view,
Synthesis and Characterization Chapter 2
64
we have synthesized some novel octa-O-methoxy resocin[4]arene derivative
containing hydrazide, chromogenic (-N=N-) groups and polymeric support through
azo-spacer (-N=N-).
3.2 Synthesis of octa- O-methoxy resorcin[4]arene tetrahydrazide via
conventional method
Synthesis of octa- O-methoxy resorcin[4]arene tetrahydrazide involves two
steps as shown in Scheme 2.
3.2.1 Octa-O-methoxy resorcin[4]arene tetraacetate derivative (2)
A mixture of octa-O-methoxy resorcin[4]arene (1) (4.8 g, 5.0 mmol) and
anhydrous potassium carbonate (10.6 g, 70 mmol), and potassium iodide (1.3 g, 8.0
mmol) in dry acetone (150 mL) was heated to reflux under nitrogen for at least 0.5
hour. Then ethyl bromoacetate (8.4 mL, 50 mmol) was added and reaction mixture
was refluxed for 7 days. After removal of acetone, the residue was dissolved in
water, acidified with HCl and extracted with CHCl3. The yellow organic layer was
separated and dried with MgSO4. Red oil was yielded after evaporation of the
solvent, which was treated with alcohol to give yellow product and was further
recrystallized from ethanol to give pure white solid compound (2).
3.2.2 Octa-O-methoxy resorcin[4]arene tetra hydrazide derivative (3)
A mixture of compound (2) (5.0 g, 3.9 mmol) and hydrazine hydrate (20 mL,
80%) in 15 mL of ethanol was refluxed for 24 hours and was then allowed to cool at
room temperature. The organic solvent was removed under vacuum. The residue
was recrystallized from ethanol to give light pink solid (3).
Synthesis and Characterization Chapter 2
65
3.3 Synthesis of octa-O-methoxy resorcin[4]arene Amberlite XAD-4 polymeric
chelating resin through azo (-N=N-) linkage (Scheme 3)
Immobilization of octa-O-methoxy resorcin[4]arene on the surface of
Amberlite XAD-4 beads was performed through azo (-N=N-) linkage to produce
octa-O-methoxy resorcin[4]arene Amberlite XAD-4 polymeric chelating resin (4) as
per the following procedure.
Step I- Nitration of Amberlite XAD-4
5.0 g of the Amberlite XAD-4 was slowly placed into a 100 mL beaker
containing a mixture of 10 mL of concentrated HNO3 and 25 mL of concentrated
H2SO4 under continuous stirring at 60°C for 1 hour on water bath. After cooling, the
mixture was transferred into a beaker containing ice-water mixture and filtered.
The obtained nitrated resin was repeatedly washed with double distilled water until
the acid was completely washed out.
Step II- Reduction of nitrated XAD-4 resin
The resulting nitrated resin was added to a mixture comprising 50 g of SnCl2,
45 mL of concentrated HCl and 50 mL of ethyl alcohol, and the content was heated
at 90°C for 12 hours under reflux to yield aminated resin. The resin was filtered and
washed with water.
Step III- Diazotization of aminated XAD-4 resin and coupling with octa-O-
methoxy resorcin[4]arene
The aminated resin was poured into the ice-water mixture and diazotizing
mixture of 1.0M HCl and 1.0M NaNO2 was slowly added at 0-5°C in aliquots of 1.0
mL each time with constant stirring until the reaction mixture showed a permanent
Synthesis and Characterization Chapter 2
66
blue color with starch-iodide paper. The resulting diazotized resin was then reacted
with octa-O-methoxy resorcin[4]arene (5.0 g dissolved in 10% NaOH) at 0-5°C for
48 hours to yield dark-brown beads, which were collected by filtration over a
sintered glass funnel. Resin was washed with methanol and water, and stored in a
glass bottle.
3.4 Synthesis of azo-octa-O-methoxy resorcin[4]arene dyes (5a, 5b)
3.4.1 General procedure for the synthesis by conventional method
The synthesis of new octa-O-methoxy resorcin[4]arene azo dyes involved the
following steps (Scheme 4).
Step I- The diazotization of aromatic primary amines ((a) Aniline, (b) O-amino
phenol)
A solution of aromatic primary amines (a, b) (0.01 mol) in 25 mL water and
0.8 mL of concentrated HCl (0.02 mol) was stirred until a clear solution was
obtained. This solution was cooled to 0-5°C and then 10 mL of sodium nitrite
solution (0.01 mol) was added dropwise, maintaining the temperature below 2°C.
The resulting mixture was stirred for 45 minutes at low temperature and
completion of reaction was checked by starch iodide paper, and the excess nitrite
was destroyed as urea.
Step II-Synthesis of azo-octa-O-methoxy resorcin[4]arene dyes (5a) and (5b)
Octa-O-methoxy resorcin[4]arene (1) (0.0010 mol) and sodium hydroxide
(0.015 mol) were dissolved in 20 mL of water and cooled to 0-5°C in a low-
temperature bath. The diazonium chloride solution of (a) or (b) was then added
gradually to the above solution. Resulting reaction mixture was stirred for an hour
Synthesis and Characterization Chapter 2
67
and allowed to keep at a low temperature for 2-4 hours to ensure completion of
reaction. The pH 6.5-7.0 was adjusted to get the dark brown/red precipitates which
was then filtered and washed with water: methanol (9:1 v/v) to obtain red/pinkish
red solid.
A sample for analysis was obtained by dissolving dark brown/red solid in 50
mL hot aqueous sodium bicarbonate (2.0 g). Activated charcoal (1.0 g) was added to
this solution, which was stirred gently and charcoal was removed by simple
filtration to get clear filtrate. The filtrate was cooled down to room temperature and
acidified with dilute HCl. The solution was again warmed up to 60°C for 30 minutes
and cooled. The resulting red/pinkish red precipitates were filtered off, washed
with water and dried in a vacuum. Yield of compounds (5a, b) were found between
60-70 %.
3.4.2 Microwave irradiation method for the synthesis
A solution of aromatic primary amines (aniline(a), O-amino phenol(b)) (0.01
mol) in 25 mL water and 0.8 mL of concentrated HCl (0.02 mol) was stirred until a
clear solution was obtained followed by addition of 10 mL of sodium nitrite solution
(0.01 mol) dropwise and the temperature was maintained between 0-5°C. The
diazotized solution was kept in CEM discover microwave synthesizer, and the
parameters of synthesizer were maintained. The diazotized amino compound was
then coupled immediately with octa-O-methoxy resorcin[4]arene (1) (1.0 gm, 1.0
mmol) in the presence of sodium hydroxide for 2.5 minutes to afford compounds
(5a,b) with 85-90 % yield.
Synthesis and Characterization Chapter 2
68
Scheme 1: Formation of octa-O-methoxy resorcin[4]arene
Scheme 2: Formation of octa-O-methoxy resorcin[4]arene tetrahydrazide
derivative
Synthesis and Characterization Chapter 2
69
Scheme 3: Synthesis of octa-O-methoxy resorcin[4]arene Amberlite XAD-4
chelating resin
Synthesis and Characterization Chapter 2
70
Scheme 4: Synthesis of azo-dyes of octa-O-methoxy resorcin[4]arene
Synthesis and Characterization Chapter 2
71
4. Result and discussion
4.1 Synthesis and spectroscopic characterization
4.1.1 Conventional and microwave assisted synthesis of octa-O-methoxy resorcin
[4]arene
A new modified protocol has been developed for the synthesis of octa-O-
methoxy resorcin[4]arene (1) (Scheme 1), which involves acid catalyzed cyclo-
condensation of 1,3 dimethoxy benzene and p-hydroxybenzaldehyde by microwave
irradiation technique. The reaction time and yield obtained by conventional method
and microwave method are compared in Table 1. The physical properties of octa-O-
methoxy resorcin[4]arene are presented in Table 2. Octa-O-methoxy
resorcin[4]arene (1) has been fully characterized by FT-IR, 1H NMR, ESI-MS, 13C
NMR and the data is reported in Table 3. Analysis of data obtained, confirms that
the octa-O-methoxy resorcin[4]arene (1) was synthesized in 10-12 hours by the
conventional method with a yield of 45-50% whereas with microwave irradiation
technique, it took only 6-8 minutes with yield of 65-70%.
In the FT-IR spectra of octa-O-methoxy resorcin[4]arene (1), –OH band
appeared at 3150 cm-1 (Figure 1). The lower value reveals that the –OH groups are
involved in intramolecular hydrogen bonding. 1H NMR of compound (1) displayed
a peak at 3.5-3.7 ppm for -OCH3, 8.7 ppm for Ar-OH and peak between 6.0- 6.7 ppm
for Ar-H (Figure 2). 13C NMR (DMSO-d6) of compound (1) displayed signal at 55.69
ppm for -OCH3, 154.3 ppm for Ar–OH and 40.0 ppm for bridge -CH (Figure 3). Mass
spectrometry (ESI-MS) 970 (M+1) is shown in Figure 4.
Synthesis and Characterization Chapter 2
72
4.1.2 Synthesis of octa- O-methoxy resorcin[4]arene tetrahydrazide derivative
Synthesis of octa- O-methoxyresorcin[4]arene tetrahydrazide involves two
steps.
In first step, reaction of octa-O-methoxy resorcin[4]arene with ethyl
bromoacetate in presence of K2CO3 and KI results in the formation of octa- O-
methoxy resorcin[4]arene tetraacetate derivative (2), which was characterized by
FT-IR, 1H NMR, ESI-MS, 13C NMR and the data is presented in Table 3. The FT-IR
spectra of compound 2 showed -C=O stretching at band 1760 cm-1 (Figure 1) and
1H NMR showed a peak at 3.5-4.5 ppm for -OCH3, 6.0-7.0 ppm for Ar-H and 1.29-1.3
ppm for Alip-CH3 (Figure 5). 13C NMR (DMSO-d6) of compound 2 displayed signal
at 14.39 ppm for –CH3, 169.56 ppm for -C=O and 65.15 ppm for -CH2 (Figure 6).
Mass spectrometry (ESI-MS) 1336 (M+Na) is shown in Figure 7.
Octa-O-methoxy resorcin[4]arene tetraacetate derivative (2), upon reaction
with hydrazine hydrate yielded octa-O-methoxyresorcin[4]arene tetrahydrazide
compound 3, which was further characterized by FT-IR, 1H NMR, ESI-MS, 13C NMR,
and the results are reported in Table 3. The FT-IR, peak at 3208 cm-1, 1585 cm-1
were assigned to –NH and –CONH group, respectively (Figure 1). 1H NMR showed a
peak at 9.2 ppm for –CONH and between 3.5-3.7 ppm for free terminal –NH2 (Figure
8). 13C NMR (DMSO-d6) of compound 3 showed signal at 166.45 ppm for –C=O, and
65.90 ppm for -CH2 and absence of signal around 14.39 ppm indicated the absence
of ester group, which confirmed the formation of hydrazide derivative of octa-O-
methoxy resorcin[4]arene (Figure 9). Mass spectrometry (ESI-MS) 1257 (M+) is
shown in Figure 10.
Synthesis and Characterization Chapter 2
73
4.1.3 Octa-O-methoxy resorcin[4]arene Amberlite XAD-4 polymeric chelating
resin
Amberlite XAD-4 (styrene-divinyl benzene copolymer) is a support widely
used to develop several polymeric chelating resins for separation and
preconcentration of trace metal ions with the aid of chelating and inorganic ligands
[28, 30]. This is also due to its good physical and chemical properties such as
porosity, surface area and durability [27]. Either the physical adsorption of
chelating ligands or covalent linkage of ligands on to polymer backbone has been
used to design the novel polymeric resins.
In view of the good complexing properties of octa-O-methoxy
resorcin[4]arene, it was thought worthwhile to couple it with Amberlite XAD-4
through an azo (–N=N–) linkage (Scheme 3). The octa-O-methoxy resorcin[4]arene
Amberlite XAD-4 polymeric chelating resin (Compound 4) was characterized by
elemental analysis, FT-IR and Mass difference. The nitrogen content in NH2-XAD-4
was found to be 2.73% higher than NO2-XAD-4, which confirms the successful
reduction of NO2-XAD-4 resin. The FT-IR spectra of nitrated Amberlite XAD-4,
intermediate NH2-XAD-4 and octa-O-methoxy resorcin[4]arene Amberlite XAD-4
chelating resin, are given in Figure 11. Asymm (N-O) and Symm (N-O) stretching
bands of the nitrated Amberlite XAD-4 were observed at 1540 and 1325 cm-1,
respectively. The N-H stretching vibrations of NH2-XAD-4 were identified with the
bands at 3400 and 1625 cm-1. The conspicuous band of –N=N- at 1470 cm-1 confirms
the formation of octa-O-methoxy resorcin[4]arene Amberlite XAD-4 chelating resin
through –N=N- linkage. Furthermore, the loading of octa-O-methoxy
Synthesis and Characterization Chapter 2
74
resorcin[4]arene (0.61 mmol g-1) on polymeric support was evaluated by mass
difference of dried resin, which also confirms the successful nitration, reduction and
coupling of diazotized Amberlite XAD-4 resin with octa-O-methoxy
resorcin[4]arene.
4.1.4 Azo dyes of octa-O-methoxy resorcin[4]arene
It has been known for many years that azo compounds are the most widely
used class of dyes due to their versatile application in various fields [31-35] such as
the dying of textile fiber, coloring of different materials, colored plastics, biological-
medical studies and advanced applications in organic synthesis. In recent years,
many diazo-coupling techniques have been designed for the synthesis of new azo-
calixarene dyes, which can also act as metal extractants [31-35]. Therefore, octa-O-
methoxy resorcin[4]arene dyes bearing –N=N– group as well as –OH groups were
synthesized by conventional as well as microwave irradiation method to enable
groups exhibit both coloring and binding properties. Synthesis of two octa-O-
methoxy resorcin[4]arene dyes (5a, b) which were obtained by coupling of
diazonium salt of aromatic amines with compound (1) by conventional as well as
microwave irradiation methods have been described. Physical properties of these
compounds are presented in (Table 2) and their complete characterization using
FT-IR, 1H-NMR, 13C NMR and elemental analysis as well as mass spectral data, which
are reported in (Table 3). The FT-IR spectra of compounds (5a, b) showed a weak
band within the range 3250-3350 cm-1 corresponding to –OH and appearance of the
band in the region 1490-1480cm-1 confirms the presence of -N=N- group (Figure
Synthesis and Characterization Chapter 2
75
12a, b). Mass spectrometry (ESI-MS) of 5a 1384 (M+) and 5b 1449 (M+1) is shown
in Figure 13 and Figure 14 respectively.
4.2 Determination of crystal structure of octa-O-methoxy resorcin[4]arene (1)
Single crystals of octa-O-methoxy resorcin[4]arene (1) was grown by slow
diffusion of methanol in DMSO solution at room temperature. A single crystal
suitable for X-ray structure analysis was obtained from a solution of DMSO (OPTEP
diagram) (Figure 15). The diffraction data were collected at 110(2) K using a
Bruker Smart-CCD diffractometer (graphite-monochromated MO Kα radiation: A
=0.071073 nm). The structure was solved via the omega-phi scan method and
refined by means of full-matrix least squares on F2. All the calculations were
performed using the SHELXTL crystallographic software package. A summary of
crystallographic relevant data and molecular structure of compound 1 is shown in
supporting data; the four methoxy benzene units in the ring were divided into two
groups with two methoxy benzene rings almost perpendicular to the other two
methoxy benzene rings, which show the resorcinarene in chair (C2h) conformation.
Conclusion
A simple, fast, efficient, and economical approach has been developed for the
formation of octa-O-methoxy resorcin[4]arene and its two azo-derivatives based on
microwave irradiation technique. Octa-O-methoxy resorcin[4]arene possessed
significant importance of binding analytes under different conditions. To improve
their binding ability, they can be functionalized with some chelating/chromogenic
groups. With this in view, we have synthesized some novel octa-O-methoxy
Synthesis and Characterization Chapter 2
76
resocin[4]arene derivative containing hydrazide, chromogenic (-N=N-) groups and
polymeric support through -N=N- bond.
Synthesis and Characterization Chapter 2
77
Table 1: Comparison of reaction time and yield obtained for octa-O-methoxy
resorcin[4]arene and its azo- derivatives by conventional and microwave method.
Table 1
Comp.
Code
Reaction time (hr/min) Yield (%)
Conventional
method
(hours)
Microwave
method
(minutes)
Conventional
method
Microwave
method
1 10-12 10-12 50 70
5a 6-7 2-4 65 90
5b 6-7 2-4 60 85
Synthesis and Characterization Chapter 2
78
Table 2: Various physical properties of octa-O-methoxy resorcin[4]arene and its
derivative
Table 2 Physical Properties
Comp.
Code
Molecular
formula
Molecular
weight
(gm)
Melting
point
(°C)
Color Analysis (%)
C H N
1 C60H56O12 969 300
(decompose)
Purple 74.50 5.80 -
2 C76H80O20 1313 >300 White 69.40 6.24
3 C68H72N8O16 1257 >300 Light
pink
64.87 5.81 8.91
5a C84H72N8O12 1384 >300 Red 71.3 5.12 8.0
5b C84H72N8O16 1448 >300 Reddish
brown
69.0 4.89 7.5
Synthesis and Characterization Chapter 2
79
Table 3: Spectroscopic characterization
Table 3 Spectroscopic characterization
Co
mp.
No.
13C NMR (δ) 1H NMR spectra
FT-IR
spectra
(cm-1)
Mass
peak
Ar-OH (δ)
-OCH3 (δ)
Ar-H (δ)
Alp-CH (δ)
Alp-CH3 (δ)
-CONH -NH2 (δ)
1 154.3,130,113.7, 79.9,55.9, 39.6
8.5 3.5-3.7 6.0-6.5
5.5 - - - 3150 (-OH)
970 ( M+1)
2 59.4,42.21, 169.56 14.39, 65.15 , 112.24,125,128
- 3.5-4.5 6.0-7.0
3.5-4.5 1.29-1.30
- - 1761 (-C=O)
1336.5 (M
+Na)
3 166.45, 155.07,130.12,114.29,95.52,79.36,65.90,56.13,39.69
- 3.0- 4.0 5.5-7.5
4.5 - 9.2 3.0-4.0
3208 (-CONH)
1257.4 (M+)
5a 129.7, 55.6,125.1, 149.5, 121.7, 95.0,130.0,133
8.5 3.53- 4.5
6.0-7.5
3.5-4.5 - - - 1485 (-N=N-)
1383.7 (M-1)
5b 118, 55.6,125.1, 149.5, 121.7, 95.0,130.0,129.7,132
7.5-8 3.53- 4.5
6.0-7.5
3.5-4.5 - - - 1486 (-N=N-)
1447.6 ( M-2)
Synthesis and Characterization Chapter 2
80
Figure 1: FT-IR of 1) Octa-O-methoxy resorcin[4]arene. 2) Octa-O-methoxy tetra
acetate resorcin[4]arene. 3) Octa-O-methoxy tetra hydazide resorcin[4]arene
Synthesis and Characterization Chapter 2
81
Figure 2: 1H NMR of octa-O-methoxy resorcin[4]arene (1)
Figure 3: 13C NMR of octa-O-methoxy resorcin[4]arene (1)
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Figure 4: Mass Spectra of octa-O-methoxy resorcin[4]arene (1)
Figure 5: 1H NMR of octa-O-methoxy resorcin[4]arene tetraacetate (2)
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Figure 6: 13C NMR of octa-O-methoxy resorcin[4]arene tetraacetate (2)
Figure 7: Mass Spectra of octa-O-methoxy resorcin[4]arene tetraacetate (2)
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Figure 8: 1H NMR of Octa-O-methoxy resorcin[4]arene tetrahydrazide (3)
Figure 9: 13C NMR of octa-O-methoxy resorcin[4]arene tetrahydrazide (3)
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Figure 10: Mass Spectra of Octa-O-methoxy resorcin[4]arene tetrahydrazide (3)
Figure 11: FT-IR spectra of 1) NO2- Amberlite XAD-4. 2) NH2-Amberlite XAD-4.
3) Octa-O-methoxy resorcin[4]arene Amberlite XAD-4 chelating resin
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Figure 12(a): FT-IR of octa-O-methoxy resorcin[4]arene aniline dye (5a)
Figure 12(b): FT-IR of octa-O-methoxy resorcin[4]arene O-amino phenol dye (5b)
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Figure 13: Mass Spectra of Octa-O-methoxy resorcin[4]arene aniline dye (5a)
Figure 14: Mass Spectra of Octa-O-methoxy resorcin[4]arene O-amino phenol dye (5b)
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Figure 15: Single crystal structure of octa-O-methoxy resorcin[4]arene (1)
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