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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