Solvent-free synthesis of trisphenols as starting precursors for the synthesis of calix[4]arenes using sulfonated multi-walled carbon nanotubes

Article abstract of DOI:10.1039/c5nj03136b

The condensation of phenol derivatives (12 substrates) with 2,6-bis(hydroxymethyl)phenols (BMP) (6 examples) is reported using sulfonated multi-walled carbon nanotubes (SO₃H@MWCNTs) under solvent-free conditions as starting precursors for the synthesis of macrocyclic molecules of calix[4]arenes. The new protocol provides a series of trisphenol derivatives (21 examples) in high yields (up to 94%) and relatively short reaction times (15-120 min). Also, direct synthesis of calix[4]arenes from different trisphenols by use of the catalyst was reported (5 examples). Furthermore, the synthesized calix[4]arene was obtained using a one-pot method from simple and easily available starting materials such as p-cresol for the synthesis of 5,11,17,23-tetramethylcalix[4]arene-25,26,27,28-tetraol. Also, in this process SO₃H@MWCNTs can be reused for seven runs with almost consistent efficiency and can be recovered by easy filtration.

Full text of DOI:10.1039/c5nj03136b

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Solvent-free synthesis of trisphenols as starting
precursors for the synthesis of calix[4]arenes
using sulfonated multi-walled carbon nanotubes†
Cite this:DOI: 10.1039/c5nj03136b
Reza Fareghi-Alamdari,* Mohsen Golestanzadeh and Negar Zekri
The condensation of phenol derivatives (12 substrates) with 2,6-bis(hydroxymethyl)phenols (BMP) (6 examples)
is reported using sulfonated multi-walled carbon nanotubes (SO3H@MWCNTs) under solvent-free conditions
as starting precursors for the synthesis of macrocyclic molecules of calix[4]arenes. The new protocol provides
a series of trisphenol derivatives (21 examples) in high yields (up to 94%) and relatively short reaction times
(15–120 min). Also, direct synthesis of calix[4]arenes from different trisphenols by use of the catalyst was
reported (5 examples). Furthermore, the synthesized calix[4]arene was obtained using a one-pot method
from simple and easily available starting materials such as p-cresol for the synthesis of 5,11,17,23-
tetramethylcalix[4]arene-25,26,27,28-tetraol. Also, in this process SO3H@MWCNTs can be reused for
seven runs with almost consistent efficiency and can be recovered by easy filtration.
Received (in Montpellier, France)
7th November 2015,
Accepted 2nd February 2016
DOI: 10.1039/c5nj03136b
www.rsc.org/njc
reports had dealt with compounds belonging to this family.
Due to their wide range of applications, there is considerable
Introduction
In recent years, phenolic compounds have become an interesting interest in the synthesis of these compounds.23–27 There have
focus of academic research because of their useful and effective been one or more disadvantages such as low yield, the produc-
properties such as anti-microbial, anti-inflammatory, and anti- tion of by-products (analogous phenolic rings), tedious work-up
atherogenic. There are many natural products with phenolic processes, and hazardous reaction conditions. It is worthwhile to
structural units such as green and black tea, and grape seeds. note that the trisphenol compounds are the precursor starting
The multi presence of the hydroxyl group in the structure of materials for the multi step synthesis of calix[4]arene. The con-
polyphenolic compounds leads to special performance features densation of paraformaldehyde/formaldehyde with p-substituted
such as antioxidant action.1–5 Trisphenol antioxidants are one of phenols affords initially cyclic oligomeric phenolic compounds
the important classes of applied antioxidants for the stabilization under alkaline conditions.27–29
of biological, industrial, and chemical systems.6,7 In spite of their
Bohmer and co-workers have extensively studied the step-
¨
wide and extensive application in various areas of industry, few wise synthesis of calix[4]arenes using two different approaches
approaches have been reported for the preparation of the men- involving the use of bisphenols and trisphenols in ‘3+1’ and
tioned compounds.8–18 Trisphenols have been synthesized in a ‘2+2’ procedures under acidic conditions (Scheme 1).30–33 The
single or multi-step process using phenol derivatives and form- ‘3+1’ approach relative to the ‘2+2’ approach is the best choice
aldehyde or paraformaldehyde. Trisphenols play an important depending on all the relative conditions such as production of
role in organic transformation especially for providing macro- component parts. Also, the use of triphenols which have been
cyclic crown ethers and calix[n]arenes.19–22
differently substituted on the trisphenol leads to a calix[4]arene
Calix[n]arenes, with their specific 3D surface, are one of the with three differently substituted phenol rings. In the ‘3+1’
well-known host supramolecules along with multi hydroxyl approach the important step is the synthesis of starting tri-
compounds such as crown ethers, cucurbiturils, cryptands, sphenols. However there are few methods for the preparation of
and cyclodextrins. A quick search using Reaxys revealed that trisphenols. In this regard, it is still a continuous challenge to
by May 2015 over 11 200 publications, patents, and technical develop active, available, nontoxic, tunable, and reusable cata-
lytic systems for the preparation of trisphenols.
Carbon nanotubes play a dual role as a catalyst support and
College of Chemistry and Chemical Engineering, Malek-Ashtar University of
a catalyst in organic transformations, due to their large specific
Technology, Tehran, 16765-3454, I. R. Iran. E-mail: reza_fareghi@yahoo.com,
surface area,34 high thermal and chemical stabilities,35,36 excel-
mohsengolestanzadeh@yahoo.com; Fax: +98 2122970195; Tel: +98 2122970277
lent electron conductivity37 and relative chemical inertness.38
† Electronic supplementary information (ESI) available. See DOI: 10.1039/
c5nj03136b
Sulfonated carbon materials especially carbon nanotubes display
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Scheme 1 The ‘‘3+1’’ and ‘‘2+2’’ convergent stepwise synthesis of calix[4]arenes.
high catalytic activity compared to their porous carbon and other from micromass; EI mode at 70 eV. Melting points were
supports.39–47 However, the SO3H group prevents the incorpora- recorded in open capillary tubes in a Barnstead electro-thermal
tion of the hydrophobic molecules and other moieties on the IA 8103 apparatus and are uncorrected. Reaction monitoring was
surface of carbon nanotubes, thereby leading to acid-catalyzed accomplished by TLC on silica gel PolyGram SILG/UV254 plates.
reaction on the support.48,49 In recent years, sulfonated carbon Elemental analysis (C, H, N) was performed using a Carlo ERBA
nanotubes have been employed in many fields such as sensors, Model EA 1108 analyzer. Also, column chromatography was
catalysts,50,51 fillers,52,53 and biomass transformation.54,55
Due to the importance of trisphenols and their utilization as
precursors for calix[4]arenes, we were interested in developing
an efficient method for the preparation of trisphenols and poly-
phenolic compounds.14,16,56–58 Herein, we aim to synthesise
trisphenols in the presence of SO3H@MWCNTs as a hetero-
geneous catalyst from 2,6-bis(hydroxymethyl)phenols (BMP)
and various substituted phenols under solvent-free conditions.
carried out on the columns of silica gel 60 (70–230 mesh).
Typical procedure for the preparation of the catalyst
5.0 g of MWCNTs and 500 mL of deionized (DI) water were
mixed and sonicated for 30 min at 40 W. Then, the solution was
filtered under reduced pressure and the obtained MWCNTs
were moved to another two-neck-flask including 100 mL of HCl
(37%) and 100 mL of HNO3 (63%) and stirred at 80 1C for 4 h
under a nitrogen atmosphere. Then, the solution was filtered
under reduced pressure and the obtained materials were com-
pletely washed with DI-water. Then, the resultant materials were
dried at 100 1C for 10 h in a vacuum oven and COOH@MWCNTs
Experimental
General
Chemicals were purchased from Fluka and Aldrich chemical were obtained. After the first step, 5.0 g of COOH@MWCNTs and
companies and used without further purification. MWCNTs 250 mL of DI-water were sonicated for 15 min at 40 W. Then, the
used in this study (L = 20–30 mm, D = 20–40 nm) have been liquid was filtered and 160 mL of H2SO4 (98%) was added to the
purchased from the Research Institute of Petroleum Industry set-up at 250–270 1C [sulfuric acid boils at 335 1C] for 20 h under
(RIPI-Iran). The known products were characterized by compar- a nitrogen atmosphere. After completion of the reaction, the
ison of their spectral and physical data with those reported in solution was cooled to room temperature and the liquid was
the literature. 1H NMR and 13C NMR spectra were obtained on a filtered and completely washed with DI-water several times until
Bruker Avance spectrometer in DMSO-d6 or CDCl3 solvents with it reached the neutral point. The functionalized CNTs were dried
tetramethylsilane (TMS) as the internal standard. FT-IR spectro- at 100 1C for 15 h in a vacuum oven. Finally, SO3H@MWCNTs
scopy (Shimadzu-8776 spectrometer) was employed for the deter- were obtained and employed in the synthesis of trisphenol and
mination of functional groups in the catalyst and final products. calix[4]arene derivatives as a heterogeneous and reusable catalyst.
Mass spectra were recorded on a platform II spectrometer These steps are described in Scheme 2.
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Scheme 2 Preparation of the heterogeneous catalytic system.
General procedure for the synthesis of trisphenols
Reusability and recovery of the catalyst
Into a canonical flask (50 mL), a mixture of BMP (3 mmol), sub- The used SO3H@MWCNTs were washed completely with chloro-
stituted phenol (9 mmol), and SO3H@MWCNTs (35 mg) were form and ethanol and dried at 100 1C for 24 h before using with
stirred at 110 1C under solvent-free conditions. After comple- fresh substances.
tion of the reaction as confirmed by TLC, the reaction mixture
was cooled to room temperature and 5 mL of acetonitrile was
added. The used catalyst was filtered over sintered glass G-4
under reduced pressure and the solvent was evaporated on a
rotary evaporator assisted by a vacuum pump. Then, the residue
was suspended in boiling water and decanted to remove the
un-reacted phenol. The product was purified by column chromato-
graphy using n-hexane : EtOAc (10 : 4) as the eluent.
Spectroscopic data of trisphenol derivatives
2,6-Bis-(2-hydroxybenzyl)-phenol (compound C1). Light brown
solid, IR (KBr): 3318, 3022, 2980, 1588, 1459, 1223 cmꢀ1. 1H-NMR
(300 MHz, DMSO-d6/TMS): 3.85 (s, 4H, CH2), 6.63 (t, 2H, J = 7.8 Hz,
H-5), 6.71 (m, 3H, phenolic), 6.81 (m, 3H, BMP), 7.005 (m, 3H,
phenolic), 0.54 (s, 1H, OH BMP), 9.58 (s, 2H, OH phenolic).
13C-NMR (75 MHz, DMSO-d6/TMS): 29.8, 114.8, 119.1, 119.3,
126.6, 127.0, 127.5, 127.8, 130.3, 152.3, 154.6. Anal. calcd for
Synthesis of calix[4]arene using trisphenols (C1, C2, C8 or C13,
C14, and C21) [3+1]
C
20H18O3: C, 78.43; H, 5.88. Found: C, 78.39; H, 5.95.
2,6-Bis-(2-hydroxy-5-methylbenzyl)-4-methylphenol (compound
In a 50 mL round bottom flask, a mixture of BMP (B1, B2, B3,
and B6) (5 mmol), trisphenol derivatives (C1, C2, C8 or C13,
C14, and C21) (5 mmol), and 70 mg of SO3H@MWCNTs was
stirred at 110 1C for appropriate time. Then, the mixture was
cooled to room temperature, and 30 mL of EtOAc was added.
In order to recover the catalyst, the mixture was heated at 50 1C
for a few minutes and the warm mixture was filtered. After
evaporation of EtOAc, a white solid was obtained in 62% yield.
C2). White solid, IR (KBr): 3265, 3090, 3000, 2919, 1604, 1505,
1392 cmꢀ1. 1H-NMR (300 MHz, DMSO-d6/TMS): 2.06 (s, 3H, CH3),
2.17 (s, 6H, CH3), 3.86 (s, 4H, CH2), 6.67–6.97 (m, 8H, BMP and
phenolic), 8.44 (s, 1H, OH BMP), 9.41 (s, 2H, OH phenolic).
13C-NMR (75 MHz, DMSO-d6/TMS): 20.1, 20.3, 29.7, 114.7, 126.7,
127.2, 127.4, 127.5, 127.6, 128.3, 130.7, 149.8, 152.2. Anal. calcd for
C23H24O3: C, 79.28; H, 6.94. Found: C, 79.45; H, 7.20.
2,6-Bis-(2-hydroxy-5-methyl-3-tert-butylbenzyl)-4-methylphenol
(compound C3). White solid, IR (KBr): 3409, 2985, 2866, 1475, 1378,
1098 cmꢀ1. H-NMR (300 MHz, DMSO-d6/TMS): 1.35 (s, 18H, tert-
One-pot synthesis of 5,11,17,23-tetramethylcalix[4]arene-
25,26,27,28-tetraol using p-cresol and BMP (B1) [1+1+1+1]
1
Bu), 2.09 (s, 9H, CH3), 3.83 (s, 4H, CH2), 6.59 (s, 2H, BMP), 6.73 (s,
In a 100 mL round bottom flask, a mixture of BMP (15 mmol) 2H, H-4 phenolic), 6.82 (s, 2H, H-6 phenolic), 8.13 (s, 2H, OH
(B1), p-cresol (15 mmol), and 200 mg of SO3H@MWCNTs was phenolic), 8.93 (s, 1H, OH BMP). 13C-NMR (75 MHz, DMSO-d6/
stirred at 110 1C for 3 h. After completion of the reaction, the TMS): 20.4, 20.7, 29.8, 30.5, 34.4, 125.0, 127.6, 127.6, 127.9, 128.5,
reaction mixture was cooled to room temperature and was 128.7, 129.1, 136.8, 149.2, 150.5. MS: m/s: 461 (72, M+), 296 (100), 284
stirred in a flask for 30 min. In order to recover the catalyst, (34), 239 (36), 133 (36), 105 (18), 57 (15). Anal. calcd for C31H40O3: C,
30 mL of EtOAc was added and the mixture was heated at 50 1C 80.83; H, 8.75. Found: C, 80.70; H, 8.37.
for 1 h and the warm mixture was filtered. After evaporation of
2,6-Bis-(5-bromo-2-hydroxybenzyl)-4-methylphenol (compound
EtOAc at room temperature, the residue was suspended in C4). White solid, IR (KBr): 3200, 2945, 1604, 1484, 1418 cmꢀ1
.
boiling water and decanted to remove the un-reacted phenol. 1H-NMR (300 MHz, DMSO-d6/TMS): 2.08 (s, 3H, CH3), 3.81
Then, the calix[4]arene was purified by column chromato- (s, 4H, CH2), 6.68 (s, 2H, 3-H BMP), 6.78 (d, 2H, J = 8.5 Hz,
graphy using n-hexane : EtOAc (10 : 5) as the eluent and a white 2-H phenolic), 7.45 (d, 2H, J = 2.2 Hz, 5-H phenolic),
solid product was obtained in 57% yield.
7.15 (dd, 2H, J = 8.5, 2.2 Hz, 3-H phenolic), 8.23 (s, 1H, OH BMP),
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9.86 (s, 2H, OH phenolic). 13C-NMR (75 MHz, DMSO-d6/TMS): 20.4, 1H-NMR (250 MHz, DMSO-d6/TMS): 3.84 (s, 4H, CH2), 6.21 (m,
29.6, 110.1, 116.9, 126.9, 128.0, 128.9, 129.4, 130.1, 132.1, 150.2, 4H, BMP and H-6 phenolic), 6.82 (d, 4H, J = 3.3 Hz, H-3, H-4
154.2. MS: m/s: 478 (67, M + 4), 474 (45, M + 2), 306 (62), 292 (96), 121 phenolic), 9.68 (br, 3H, OH BMP and phenolic). 13C-NMR
(76), 108 (100). Anal. calcd for C21H18Br2O3: C, 52.75; H, 3.79. Found: (62.5 MHz, DMSO-d6/TMS): 29.6, 110.1, 117.0, 122.9, 127.2, 128.9,
C, 52.59; H, 3.57.
2,6-Bis-(5-chloro-2-hydroxybenzyl)-4-bromophenol (compound 48.18, H, 3.03. Found: C, 48.27; H, 3.19.
C5). Pale-yellow solid, IR (KBr): 3153, 2950, 1602, 1490, 1457 cmꢀ1
2,6-Bis-(5-fluoro-2-hydroxybenzyl)-4-fluorophenol (compound
129.4, 129.8, 132.4, 151.4, 154.3. Anal. calcd for C20H15Br2ClO3: C,
.
1H-NMR (300 MHz, DMSO-d6/TMS): 3.82 (s, 4H, CH2), 6.83 (d, C12). White solid, IR (KBr): 3318, 1588, 1491, 1459 cmꢀ1
.
2H, J = 8.5 Hz, 2-H phenolic), 6.94 (s, 2H, 3-H BMP), 7.00 (d, 2H, 1H-NMR (300 MHz, DMSO-d6/TMS): 3.83 (s, 4H, CH2), 6.60
J = 2.3 Hz, 5-H phenol), 7.07 (dd, 2H, J = 8.5, 2.3 Hz, 3-H (d, 2H, J = 9.3 Hz, BMP), 6.77–6.88 (m, 6H, phenolic), 8.45 (s,
phenolic), 8.81 (s, 1H, OH BMP), 9.87 (s, 2H, OH phenolic). 1H, OH BMP), 9.56 (s, 2H, OH phenolic). 13C-NMR (75 MHz,
13C-NMR (75 MHz, DMSO-d6/TMS): 29.5, 110.8, 116.4, 122.4, DMSO-d6/TMS): 30.0, 113.2 (d, 2JC–F = 22.3 Hz), 113.8 (d, 2JC–F
126.9, 128.3, 129.5, 130.0, 130.1, 151.9, 153.9. Anal. calcd for 22.4 Hz), 115.6 (d, JC–F = 7.9 Hz), 116.3 (d, JC–F = 22.6 Hz),
=
3
2
3
3
C20H15BrCl2O3: C, 52.90; H, 3.33. Found: C, 52.79; H, 3.18.
127.9 (d, JC–F = 7.0 Hz), 129.3 (d, JC–F = 7.5 Hz), 148.6, 151.1,
2,6-Bis-(5-chloro-2-hydroxybenzyl)-4-fluorophenol (compound 155.5 (d, 1JC–F = 232.1 Hz), 155.6 (d, 1JC–F = 232.7 Hz). Anal. calcd
C6). White solid, IR (KBr): 3228, 2945, 1610, 1487 cmꢀ1
1H-NMR (300 MHz, DMSO-d6/TMS): 3.82 (s, 4H, CH2), 6.61 (d,
.
for C20H15F3O3: C, 66.67; H, 4.20. Found: C, 66.71; H, 4.24.
2,6-Bis-(5-chloro-2-hydroxybenzyl)-4-methylphenol (compound
2H, 2-H phenolic), 6.82 (dd, 2H, 3-H phenolic), 6.98 (d, 2H, 5-H C13). White solid, IR (KBr): 3135, 3030, 2930, 1600, 1485, 1420,
phenolic), 7.07 (dt, 2H, 3-H BMP), 8.46 (s, 1H, OH BMP), 9.85 (s, 1390 cmꢀ1. 1H-NMR (250 MHz, DMSO-d6/TMS): 2.06 (s, 3H, CH3),
2H, OH phenolic). 13C-NMR (75 MHz, DMSO-d6/TMS): 29.8, 3.8 (s, 4H, CH2), 6.63–7.19 (m, 8H, BMP and phenolic), 8.32 (s,
113.9 (d, 2JC–F = 22.4 Hz), 116.4, 122.4, 126.9, 128.3, 128.5, 129.2 1H, OH BMP), 9.8 (s, 2H, OH phenolic). 13C-NMR (62.5 MHz,
(d, 3JC–F = 7.5 Hz), 129.50, 153.9, 155.9 (d, 1JC–F = 233.2 Hz). Anal. DMSO-d6/TMS): 20.3, 29.6, 116.2, 122.3, 126.4, 126.7, 127.7,
calcd for C20H15Cl2FO3: C, 61.09; H, 3.85. Found: C, 60.79; H, 3.69. 128.0, 129.2, 129.5, 144.9, 153.7. Anal. calcd for C21H18Cl2O3: C,
2,6-Bis-(5-chloro-2-hydroxybenzyl)-4-chlorophenol (compound 64.80; H, 4.66. Found: C, 64.73, H, 4.59.
C7). Yellow solid, IR (KBr): 3150, 3010, 2980, 1610, 1220 cmꢀ1
.
2,6-Bis-(2,5-dihydroxybenzyl)-4-chlorophenol (compound C14).
1H-NMR (300 MHz, DMSO-d6/TMS): 3.82 (s, 4H, CH2), 6.67–7.09 Light-brown crystals, IR (KBr): 3200, 3020, 2990, 1610, 1600, 1500,
(m, 8H, aromatic), 8.88 (s, 1H, OH BMP), 9.82 (s, 2H, OH 1450, 1250, 850 cmꢀ1. 1H-NMR (250 MHz, DMSO-d6/TMS): 3.89 (s,
phenolic). 13C-NMR (75 MHz, DMSO-d6/TMS): 29.6, 116.4, 122.4, 4H, CH2), 6.50 (m, 4H, H-3, H-4 phenolic), 6.61 (s, 2H, H-BMP),
122.8, 126.9, 127.2, 128.4, 129.4, 129.5, 151.4, 153.9. Anal. calcd for 6.87 (s, 2H, H-6 phenolic), 8.77 (s, 2H, OH-5 phenoic), 8.88 (s, 1H,
C20H15Cl3O3: C, 58.64; H, 3.69. Found: C, 58.55; H, 3.52.
2,6-Bis-(2-hydroxy-5-methylbenzyl)-4-chlorophenol (compound DMSO-d6/TMS): 29.7, 113.6, 115.5, 116.8, 122.7, 126.7, 126.8,
C8). White solid, IR (KBr): 3208, 3018, 2876, 1605, 1448, 810 cmꢀ1
130.0, 147.0, 149.7, 151.2. Anal. calcd for C20H17ClO5: C, 64.44;
1H-NMR (250 MHz, DMSO-d6/TMS): 2.13 (s, 6H, CH3), 3.77 (s, 4H, H, 4.60. Found: C, 64.40; H, 4.54.
OH BMP), 9.00 (s, 2H, OH-2 phenolic). 13C-NMR (62.5 MHz,
.
CH2), 6.38–7.12 (m, 8H, aromatic), 8.69 (s, 1H, OH BMP), 9.34 (s,
2,6-Bis-(2-hydroxy-5-nitrobenzyl)-4-chlorophenol (compound
2H, OH phenolic). 13C-NMR (62.5 MHz, DMSO-d6/TMS): 20.14, C15). Yellow solid, IR (KBr): 3400, 3090, 2920, 1630, 1590, 1500,
29.6, 114.8, 122.6, 125.6, 126.6, 127.5, 127.6, 130.1, 130.9, 151.1, 1300 cmꢀ1 1H-NMR (250 MHz, DMSO-d6/TMS): 3.93 (s, 4H,
.
152.4. Anal. calcd for C22H21ClO3: C, 71.64; H, 5.74. Found: C, CH2), 6.96 (m, 4H, BMP and H-3 phenolic), 7.98 (m, 4H, H-4,
71.73; H, 5.86.
H-6 phenolic), 9.05–10.48 (s br, 3H, OH BMP and phenolic).
2,6-Bis-(5-fluoro-2-hydroxybenzyl)-4-chlorophenol (compound 13C-NMR (62.5 MHz, DMSO-d6/TMS): 29.6, 115.0, 122.1, 124.0,
C9). White solid, IR (KBr): 3190, 3045, 2945, 1600, 1495, 1445, 125.7, 127.5, 129.0, 129.4, 139.4, 151.6, 161.7. Anal. calcd for
1235, 1190 cmꢀ1. 1H-NMR (250 MHz, DMSO-d6/TMS): 3.80 (s, 4H, C20H15ClN2O7: C, 55.76, H, 3.51. Found: C, 55.67, H, 3.40.
CH2), 6.77–7.09 (m, 8H, aromatic), 8.75 (s, 1H, OH BMP), 9.57
2,6-Bis-(2-hydroxy-5-phenylbenzyl)-4-chlorophenol (compound
(s, 2H, OH phenolic). 13C-NMR (62.5 MHz, DMSO-d6/TMS): 29.7, C16). White solid, IR (KBr): 3200, 3030, 2910, 1610, 1600, 1520,
113.1, 113.4, 115.5, 116.1, 122.9, 127.1, 127.6, 129.5, 151.3, 153.5, 1490, 1220 cmꢀ1. 1H-NMR (250 MHz, DMSO-d6/TMS): 3.54 (s, 4H,
157.2. Anal. calcd for C20H15ClF2O3: C, 63.76; H, 4.01. Found: C, CH2), 6.7–7.61 (m, 18H, aromatic), 8.82 (s br, 3H, OH BMP and
63.67; H, 3.92.
2,6-Bis-(5-bromo-2-hydroxybenzyl)-4-bromophenol (compound 125.2, 125.8, 125.9, 126.7, 128.3, 128.6, 129.7, 129.8, 130.9, 140.6,
C10). Yellow solid, IR (KBr): 3200, 3090, 2950, 1600, 1250 cmꢀ1
157.2, 159.7. Anal. calcd for C32H25ClO3: C, 77.96; H, 5.11. Found:
1H-NMR (250 MHz, DMSO-d6/TMS): 3.81 (s, 4H, CH2), 6.79 (d, 2H, C, 78.11; H, 5.22.
phenolic). 13C-NMR (62.5 MHz, DMSO-d6/TMS): 33.4, 115.7, 117.3,
.
J = 4.7 Hz, H-6 phenolic), 6.98 (s, 2H-BMP), 7.13–7.19 (m, 4H, H-3,
6,60-[(5-Chloro-2-hydroxy-1,3-phenylene)bis(methylene)]bis-
H-4 phenolic), 8.80 (s, 1H, OH BMP), 9.89 (s, 2H, OH phenolic). (4-allyl-2-methoxyphenol) (compound C17). Pale-yellow solid;
13C-NMR (62.5 MHz, DMSO-d6/TMS): 29.4, 110.0, 110.7, 117.0, IR (KBr): 3450, 3090, 2950, 2985, 1600, 1510, 1450 cmꢀ1
.
128.9, 129.8, 129.9, 130.0, 132.3, 151.8, 154.3. Anal. calcd for 1H NMR (250 MHz, DMSO-d6/TMS): 3.16 (d, J = 6.6 Hz, 4H,
C20H15Br3O3: C, 44.24; H, 2.78. Found: C, 44.13; H, 2.59. Ar–CH2–CHQ), 3.63 (s, 4H, Ar–CH2–Ar), 3.72 (s, 6H, OCH3),
2,6-Bis-(5-bromo-2-hydroxybenzyl)-4-chlorophenol (compound 4.83 (dd, J = 16.5, 10.3 Hz, 4H, QCH2), 4.89 (s, 3 H, OH BMP
C11). White solid, IR (KBr): 3150, 3020, 2990, 1600, 1220 cmꢀ1
and phenolic), 5.72 (m, 2 H, Ar–CH2–CHQCH2), 6.89–7.31
ꢀ ꢀ
ꢀ ꢀ
.
ꢀ ꢀ
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(m, 6H, BMP and phenolic). 13C NMR (62.5 MHz, DMSO-d6/TMS): 7.98 (d, 8H, aromatic), 9.93 (s, 4H, OH). 13C NMR (100 MHz,
30.1, 40.0, 56.4, 111.3, 115.4, 117.5, 122.7, 124.4, 125.9, 128.7, 134.0, CDCl3/TMS): 34.6, 127.0, 134.3, 136.3, 138.3. Anal. calcd for
138.8, 141.7, 143.0, 156.3. Anal. calcd for C28H29ClO5: C, 69.92; H, C28H24O4: C, 79.23; H, 5.70. Found: C, 78.87; H, 5.59.
6.08. Found: C, 70.01; H, 6.15.
5,17-Dichloro-11,23-dimethylcalix[4]arene-25,26,27,28-tetraol
6,60-[(5-Bromo-2-hydroxy-1,3-phenylene)bis(methylene)]bis- (compound D3). White solid; Mp: 315–317 1C. IR (KBr): 3242,
(4-allyl-2-methoxyphenol) (compound C18). Light-brown solid; 2925, 1503, 1454, 1223, 1101, 812. 1H NMR (400 MHz, CDCl3/TMS):
IR (KBr): 3450, 3087, 2953, 2982, 16 594, 1516, 1432, 1198 cmꢀ1
.
2.09 (s, 6H, CH3), 3.73 (d, 4H, CH2), 4.02 (d, 4H, CH2), 6.59 (s, 4H,
1H NMR (250 MHz, DMSO-d6/TMS): 3.36 (d, J = 6.4 Hz, 4H, aromatic), 6.82 (s, 4H, aromatic), 8.73 (s, 2H, OH), 9.67 (s, 2H, OH).
Ar–CH2–CHQ), 3.86 (s, 4H, Ar–CH2–Ar), 4.39 (s, 6H, OCH3), 13C NMR (100 MHz, CDCl3/TMS): 27.5, 37.3, 119.3, 121.2, 127.5,
ꢀ ꢀ
ꢀ ꢀ
5.03 (dd, J = 16.8, 10.3 Hz, 4H,QCH2), 5.15 (s, 3H, OH BMP and 129.1, 130.1, 132.6, 137.0, 141.6. Anal. calcd for C30H26Cl2O4: C,
phenolic), 5.96 (m, 2H, Ar–CH2–CHQCH2), 6.47–7.33 (m, 6H, 69.10; H, 5.03. Found: C, 69.31; H, 5.29.
ꢀ ꢀ
BMP and phenolic). 13C NMR (62.5 MHz, DMSO-d6/TMS): 29.6,
5,17-Dichloro-11,23-dihydroxycalix[4]arene-25,26,27,28-tetraol
40.4, 56.5, 111.4, 115.3, 117.7, 122.7, 124.4, 125.8, 128.7, 134.5, (compound D4). White solid; Mp: 295–298 1C. IR (KBr): 3345,
1
138.3, 141.3, 143.2, 154.4. Anal. calcd for C28H29BrO5: C, 64.01; 3298, 3010, 2984, 2875, 1541, 1458, 1225, 1112, 845. H NMR
H, 5.56. Found: C, 64.09; H, 5.61.
(400 MHz, CDCl3/TMS): 3.76 (s, 4H, CH2), 4.12 (s, 4H, CH2), 6.59
1,10-{[(5-Fluoro-2-hydroxy-1,3-phenylene)bis(methylene)]bis- (s, 4H, aromatic), 6.86 (s, 4H, aromatic), 8.75 (s, 4H, OH), 9.65
(5-fluoro-2-hydroxy-3,1-phenylene)}bis(ethan-1-one) (compound (s, 2H, OH). 13C NMR (100 MHz, CDCl3/TMS): 27.5, 119.3, 121.2,
C19). Light-yellow solid; IR (KBr): 3460, 3085, 2980, 1600, 1450, 127.5, 129.1, 130.2, 133.6, 136.9, 142.6. Anal. calcd for C28H22Cl2O6:
1211, 1095, 1005, 950 cmꢀ1. 1H NMR (250 MHz, DMSO-d6/TMS): C, 64.01; H, 4.22. Found: C, 64.38; H, 4.56.
2.64 (s, 6 H, CH3–Ac), 3.92 (s, 4H, CH2), 6.61–6.65 (s, 2H, BMP),
5,11,17,23-Tetra-tert-butylcalix[4]arene-25,26,27,28-tetraol (com-
7.10–7.20 (m, 2H, H-6 phenolic), 7.67 (dd, J = 8.6, 2.2 Hz, 2H, H-4 pound D5). White solid; Mp: 333–336 1C. IR (KBr): 3358, 3001,
phenolic), 8.56 (s, 1H, OH BMP), 8.89 (s, 1H, OH phenolic), 12.41 2994, 2895, 1501, 1418, 1255, 1102, 745. 1H NMR (400 MHz,
(s, 1H, OH phenolic). 13C NMR (62.5 MHz, DMSO-d6/TMS): 27.1, CDCl3/TMS): 1.27 (s, 36H, tert-butyl), 3.57 (s, 4H, CH2), 4.27 (s, 4H,
29.3, 114.0, 114.3, 114.7, 118.7, 123.6, 124.0, 127.5, 128.5, 130.6, CH2), 7.43 (s, 8H, aromatic), 9.59 (s, 4H, OH). 13C NMR (100 MHz,
148.8, 151.9, 155.7, 205.3. Anal. calcd for C24H19F3O5: C, 64.86; CDCl3/TMS): 33.1, 34.1, 36.4, 128.9, 130.1, 141.8, 148.6. Anal. calcd
H, 4.31. Found: C, 64.69; H, 4.16.
for C44H56O4: C, 81.44; H, 8.70. Found: C, 81.04; H, 8.56.
6,60-[(5-Chloro-2-hydroxy-1,3-phenylene)bis(methylene)]bis-
(2-tert-butyl-4-methylphenol) (compound C20). White solid; IR
(KBr): 3552, 3510, 2995, 2915, 1445, 1170, 1090, 1020, 870 cmꢀ1
.
Results and discussion
Catalyst preparation
1H NMR (250 MHz, DMSO-d6/TMS): 1.38 (s, 18H, tert-butyl),
2.11 (s, 6H, CH3), 3.95 (s, 4H, CH2), 6.61–6.97 (m, 6H, BMP and
phenolic), 7.45 (s, 1H, OH BMP), 8.12 (s, 2H, OH phenolic).
13C NMR (62.5 MHz, DMSO-d6/TMS): 20.9, 29.6, 32.2, 35.1, 126.0,
127.5, 127.8, 128.5, 131.6, 131.8, 135.0, 137.9, 147.2, 151.1. Anal.
calcd for C30H37ClO3: C, 74.90; H, 7.75. Found: C, 74.99; H, 7.81.
2,6-Bis-(2-hydroxy-5-tert-butylbenzyl)-4-tert-butylphenol (com-
pound C21). White solid; IR (KBr): 3360, 3087, 2919, 1604, 1505,
1392 cmꢀ1. 1H NMR (250 MHz, DMSO-d6/TMS): 1.45 (s, 27H, tert-
butyl), 3.86 (s, 4H, CH2), 6.63–6.93 (m, 8H, BMP and phenolic),
8.13 (s, 1H, OH BMP), 8.93 (s, 2H, OH phenolic). 13C NMR (62.5
MHz, DMSO-d6/TMS): 29.8, 30.5, 34.4, 124.9, 127.6, 127.8, 128.5,
129.1, 136.7, 149.2, 150.5. Anal. calcd for C32H42O3: C, 80.97; H,
8.92. Found: C,80.12; H, 8.14.
As shown in Scheme 2, the heterogeneous SO3H@MWCNT
catalyst was prepared in two sequential steps. First, MWCNTs were
converted to COOH@MWCNTs based on the reported literature.59,60
Table 1 Optimization of the reaction conditions
Catalyst
Entry (mg)
BMP
p-Cresol
Yielda
(%)
Solvent
(mmol) (mmol) T (1C) Time
Spectroscopic data of calix[4]arene derivatives
1
2
3
4
5
6
7
8
—
35
35
35
35
35
35
35
35
35
35
25
20
H2O
H2O
CH3CN
CH3CN/H2O 3
Solvent-free
Solvent-free
Solvent-free
Solvent-free
Solvent-free
Solvent-free
Solvent-free
Solvent-free
Solvent-free
3
3
3
6
6
6
6
6
6
6
6
7.5
9
Reflux 48 h
Reflux 24 h
Reflux 2 h
Reflux 2 h
0
5,11,17,23-Tetramethylcalix[4]arene-25,26,27,28-tetraol (com-
Trace
40
35
45
55
pound D1). White solid; Mp: 322–324 1C. IR (KBr): 3238, 2920,
1615, 1510, 1389, 1228, 1115, 815 cmꢀ1 1H NMR (400 MHz,
.
3
3
3
3
3
3
3
3
3
50
70
90
2 h
2 h
1 h
CDCl3/TMS): 2.17 (s, 12H, CH3), 3.57 (s, 4H, CH2), 4.27 (s, 4H,
CH2), 7.49 (s, 8H, aromatic), 9.66 (s, 4H, OH). 13C NMR (100 MHz,
CDCl3/TMS): 21.1, 34.1, 128.5, 128.9, 130.1, 136.8, 148.0. Anal.
calcd for C32H32O4: C, 79.97; H, 6.71. Found: C, 80.12; H, 6.14.
Calix[4]arene-25,26,27,28-tetraol (compound D2). White solid;
Mp: 311–313 1C. IR (KBr): 3265, 3020, 2919, 2861, 1691, 1604,
1505, 1236, 1137, 809. 1H NMR (400 MHz, CDCl3/TMS):
3.71 (d, 4H, CH2), 4.05 (d, 4H, CH2), 8.65 (t, 4H, aromatic),
73
110
110
110
110
110
110
45 min 85
45 min 89
25 min 94
25 min 94
1 h
2 h
9
10
11
12
13
10.5
9
9
77
55
a
Isolated yields.
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Table 2 Synthesis of trisphenol derivativesa
Entry x-Phenol
BMP
Trisphenol
Time (min) Yieldb (%) TOFc (hꢀ1
)
M.p. (1C) ref.
1
20
25
91
87
43.8
33.2
213–214 16
2
3
214–216 16
170–172 16
30
86
27.3
4
5
6
7
30
40
45
35
92
86
84
89
29.2
20.7
17.8
24.2
234–236 16
234–236 16
205–207 16
234–235 14
8
9
30
40
90
86
28.6
20.7
137–138 15
222–224 15
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Table 2 (continued)
Entry x-Phenol
BMP
Trisphenol
Time (min) Yieldb (%) TOFc (hꢀ1
)
M.p. (1C) ref.
10
40
40
45
35
15
40
87
86
84
89
87
82
20.9
20.7
17.8
24.2
55.2
19.7
237–239 14
11
12
13
14
15
251–253 18
238–239 18
235–237 17
178–180 17
220–221 18
16
17
40
45
84
79
20.2
16.7
146–147 14
55–56 14
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Table 2 (continued)
Entry x-Phenol
BMP
Trisphenol
Time (min) Yieldb (%) TOFc (hꢀ1
)
M.p. (1C) ref.
18
45
77
16.3
58–60 14
19
20
120
30
75
90
5.9
28.6
16.7
143–145 18
191–193 16
140–142
21
45
79
a
b
c
General reaction conditions: x-phenol (9 mmol), BMP (3 mmol), 110 1C, solvent-free, catalyst (35 mg). Isolated yields. Turn over frequency.
Second, COOH@MWCNTs were reacted with sulfuric acid to obtain when acetonitrile was used as solvent (Table 1, entry 3). In order
SO3H@MWCNTs. It is notable that the prepared catalyst is not to improve the conditions, combined solvents were employed
soluble in all organic solvents due to the properties and hydro- (H2O:CH3CN). In this experiment, no improvement in yield and
phobicity of carbon nanotubes; it has acceptable reactivity time of the reaction was observed and the model reaction was
and stability compared to other solid acid catalysts.39,42 Also, investigated under solvent-free conditions (Table 1, entry 5). As
SO3H@MWCNTs are very stable substrates to above 200 1C shown in this entry, the yield of C3 was increased to 45% and
based on thermogravimetric analysis (see Fig. S5, ESI†). The reaction time was decreased to 2 h. In accordance with these
details of the preparation of the catalyst are shown in Scheme 2 results, the model reaction was carried out under solvent-free
and the Experimental section. The SO3H@MWCNT catalyst has conditions for further experiments.
been fully characterized using microscopic and spectroscopic
Additionally, the effect of temperature was studied in the
model reaction (Table 1, entries 5–8). It was observed that an
increase in the temperature of the reaction up to 110 1C
increased the yield of the desired product up to 85% (Table 1,
techniques61 and is available in the ESI.†
Optimization of the reaction conditions
The reaction between BMP (B2) and p-cresol (A2) was chosen as entry 8). At this temperature (110 1C), the time of the reaction
a model reaction in order to evaluate the effects of solvents, was decreased to 45 min. Then, the molar ratios of substrates
temperature, molar ratio and the amount of catalyst. The results were changed (Table 1, entries 9–11). It was found that the best
of optimization studies are shown in Table 1. It was found that, molar ratio was 3 : 1 (p-cresol : BMP) and the consumption of
when the reaction was carried out without any catalyst, no desired BMP was 100%.
product was obtained even after 48 h (Table 1, entry 1). In order
Finally, the amount of catalyst was determined and the
to obtain the best conditions for the model reaction, in our results are summarized in entries 12 and 13. It was observed
initial selection, water was used as the solvent. In this test, that with a decreasing amount of the catalyst the yield of the
trisphenol (C3) was obtained in trace after 24 h (Table 1, entry 2). reaction decreased to 77 and 55%. According to Table 1, the best
It was observed that, the yield of C3 was enhanced to 40%, amount of catalyst was 35 mg in the model reaction.
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Scheme 3 Synthesis of calix[4]arenes (D1–D5) using the [3+1] approach.
Scheme 4 One-pot synthesis of calix[4]arene (D1).
After optimization, a range of trisphenol derivatives (C1–C21) When p-cresol was used, different BMPs such as B2 and B3 were
were obtained using the SO3H@MWCNT catalyst under obtained tested in the synthesis of trisphenols. As shown in these entries
optimum conditions (Table 2). We started our investigation using (2 and 8), BMP with electron withdrawing substituents was
different substituted phenols (A1–A12) and various BMPs (B1–B6) better than BMP with electron donating substituents. The high
in the presence of the SO3H@MWCNT catalyst under solvent-free density of electrons on the phenol ring such as 2-tert-butyl-4-
conditions. Table 2 shows that the SO3H@MWCNT catalyst is an methyl phenol (A3) caused the yield of the reaction to increase
effective catalyst for the synthesis of trisphenols (C1–C21). As to 90% (Table 2, entry 20). Also, hydroquinone (A8) reacted with
shown in this table, the catalytic activity of SO3H@MWCNTs BMP (B3) to produce C14 in 87% yield (Table 2, entry 14).
depended on the types of groups (electron donating or electron
withdrawing) on the phenol ring.
Additionally, phenol derivatives with electron withdrawing
groups were used in the synthesis of trisphenols. For example,
Electron donating substituents on the phenol ring like 4-bromophenol (A4) was treated with various BMPs such as B2,
methyl or hydroxyl groups (Table 2, entries 8 and 14) produced B3, and B4 (Table 2, entries 4, 10 and 11). It was found that
the corresponding trisphenols in good yields (87% and 90%). BMP with methyl substituents (entry 4) resulted in a higher
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Scheme 5 The proposed mechanism for the preparation of trisphenol and calix[4]arene using sulfonated multi-walled carbon nanotubes as catalysts.
yield (92%), while BMP with electron withdrawing groups such as according to the reported literature.64 In this experiment,
bromo and chloro generated trisphenols (A10, A11) in 87% and calix[4]arene (D1) was produced in 57% yield (Scheme 4).
86% yields respectively. Furthermore, 4-chlorophenol (A6) and
We propose the following plausible mechanism for the pre-
4-flurophenol (A7) were investigated in the presence of different paration of trisphenol and calix[4]arene subsequently. Activation
BMPs. It was observed that A6 with B3 produced trisphenol in 89% of BMP (I) is done using SO3H@MWCNTs. Simultaneously,
yield (entry 7), while trisphenol (C9) was generated in 86% yield by SO3H@MWCNTs as a robust Bronsted acid assists the activation
the reaction of A7 with B3 (entry 9). Therefore, the electron of (I) to give (II). The nucleophilic attack of two molecules of
withdrawing groups on the phenol ring caused the yield of the p-substituted phenol from the ortho-position on (II) affords (IV),
reaction to decrease. Our results were confirmed by two entries of which is subsequently converted to trisphenol (V) as the final
this table (Table 2, entries 15 and 16). 4-Nitrophenol (A9) and product. In this case, trisphenol (V) can be reacted with the
4-phenylphenol (A10) were reacted with BMP (B3). In these experi- intermediate (II), which was generated by the activation of (I)
ments, the time of the reaction was increased because of the using the catalyst, to produce intermediate (VI). This intermediate
electron withdrawing substituent groups on the phenol ring.
By employing the developed protocol, 4-allyl-2-methoxyphenol
(A11) was reacted with two types of BMP (B3 and B4) (Table 2,
entries 17 and 18). The results show that B3 is better than B4 and
electron withdrawing groups on the BMP ring improve the yield of
the reaction. Finally, substituted acetophenone (A12) was employed
in the synthesis of trisphenol (C19) (Table 2, entry 19). As can be
seen, substituted acetophenone with low electron density resulted
in the production of trisphenol in moderate yield (75%) in 120 min.
After preparation of trisphenol derivatives, we wish to synthesise
different calix[4]arene derivatives (D1–D5) as macrocyclic molecules
using different trisphenols (C1, C2, C8 or C13, C14, and C21) and
BMP (B1, B2, B3, and B6) (Scheme 3). In this experiment, symme-
trical calix[4]arenes with the same or different groups were pro-
duced in 65–82% yield. Therefore, we can synthesise a range of
symmetrical and asymmetrical calix[4]arenes via this protocol in
the presence of the SO3H@MWCNT catalyst. These calix[4]arenes
have a wide range of applications in many fields of science.62,63
We also synthesized calix[4]arene (D1) by one-pot reaction using
simple and readily available materials such as p-cresol. BMP was
can be converted to calix[4]arene (VII) (Scheme 5).
Reusability and recyclability of the catalyst
The recyclability of the SO3H@MWCNT catalyst for this protocol
was also studied in the multiple sequential reaction of B2 and A3
and the results showed that this catalyst was recovered by easy
filtration and reused without remarkable loss of catalytic activity
for seven runs (Fig. 1).
synthesized from the substituted phenol and formaldehyde Fig. 1 Reusability of the catalyst in the synthesis of trisphenol C4.
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Table 3 Comparison of the results obtained for the synthesis of compound D1 with those obtained by the reported studies
Entry
Starting materials
Reaction conditions
Yield (%)
Ref.
65
THF, acetic acid, H2O/24 h/ambient temperature,
CH3I, NaBH4, DMSO, 30 min., R.T., then 80 1C
1
72
67
SnCl4, CHCl3, ambient temperature,
LiAlH4, THF, R.T.
2
66
NaBH4, CH3I, DMSO, 30 min., R.T.,
then 80 1C
3
69
65
4
LiAlH4, THF, ambient temperature, 20 h
79
66
5
6
NaOH, Pd/charcoal, HCl
58
67
67
68
KOC(CH3)3, xylene, reflux, 6 h
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Table 3 (continued)
Entry
7
Starting materials
Reaction conditions
Yield (%)
Ref.
One-pot: MWCNT–SO3H, 110 1C,
solvent-free
57
72
This work
8
MWCNT–SO3H, 110 1C, solvent-free
This work
3 S. F. Parker, Chem. Commun., 2011, 47, 1988–1990.
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2002, 41, 3656–3667.
In order to show the efficiency and advantage of the present
method in the synthesis of calix[4]arenes, we have compared the
obtained results in the synthesis of 5,11,17,23-tetra-methylcalix-
[4]arene-25,26,27,28-tetraol (D1) catalyzed by MWCNTs–SO3H
with those of some reported studies in the literature (Table 3).
It seems that the presented new method is superior in terms of
the catalyst amount, reusable catalyst, time of the reaction,
reaction temperature, use of organic solvents and product yield.
Conclusion
8 D. J. Beaver, R. S. Shumard and P. J. Stoffel, J. Am. Chem.
Soc., 1953, 75, 5579–5581.
In conclusion, the present study shows that sulfonated multi-
walled carbon nanotubes can be employed as a robust and
reusable catalyst for the preparation of trisphenol derivatives. The
catalyst can be prepared using a simple procedure from commer-
cially available starting materials. Also, we have developed a new
approach for the synthesis of trisphenol derivatives by the reac-
tion of 2,6-bis(hydroxymethyl)phenols with p-substituted phenol
under solvent-free conditions. Furthermore, from the trisphenol
derivatives, different calix[4]arenes were synthesized in 65–82%
yield. The new approach could be used for the one-pot synthesis
of calix[4]arenes from simple starting materials.
9 L. K. Popov, F. M. Egidis and V. V. Ershov, Bull. Acad. Sci.
USSR, Div. Chem. Sci., 1968, 17, 863–865.
10 G. Ferguson, W. Bell, P. I. Coupar and C. Glidewell, Acta
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´
´ˇ
11 J. Lerchova and J. Pospısil, Die Angew. Makromole. Chem.,
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12 G. H. Hakimelahi and A. A. Moshfegh, Helv. Chim. Acta,
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13 A. A. Moshfegh, B. Mazandarani, A. Nahid and G. H.
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14 R. Fareghi-Alamdari, A. Khalafi-Nezhad and N. Zekri,
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15 A. Khalafi-Nezhad, M. N. S. Rad and G. H. Hakimelahi, Helv.
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Acknowledgements
We thank the Malek-Ashtar University of Technology for sup-
port of this work.
17 A. Khalafi-Nezhad, A. Parhami, R. Bargebid, S. Molazade,
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