Int. J. Chem. Sci.

: 8(5), 2010, S578-S584

SYNTHESIS OF ANTIOXIDANTS : GREEN CHEMISTRY

ROUTE
PANDIAN ELAVARASAN, KISHORE KONDAMUDI and
SREEDEVI UPADHYAYULA*

Department of Chemical Engineering, Indian Institute of Technology, NEW DELHI 110016, INDIA

ABSTRACT
Butylated hydroxytoluene (BHT) and tert-butylated phenols were chemically synthesized using a
green catalyst. Freshly prepared ionic liquid catalyst, N-(1,4-sulfonic acid) butyl triethylammonium
hydrogen sulfate and butylation of phenols conducted in batch reactor with autogeneous pressure. The
major product of alkylated phenol is 2, 4-di-tert-butyl phenol and 2, 6-di-tert-butyl p-cresol (BHT) was
obtained at 70C.

Key words: Alkylation, Ionic liquid, Phenol p- cresol, Tert-butyl alcohol, BHT, 2, 4-DTBP.

INTRODUCTION
Alkylated phenols are well known antioxidants. In particular, butylated phenol and
butylated hydroxytoluene (BHT) are major antioxidants used in the food industry1-9. Both
homogenous and heterogeneous catalyst have been reported for alkylation of phenols, which
include Lewis acid AlCl3 and BF310, Bronsted acids such as H3PO3, H2SO4, HF and HClO311,
cation exchange resin7, zeolites2-4, mesoporous materials3,9, heteropoly acid 10, super critical and
near critical water5. The major draw backs of liquid acid catalysts are hazardous and corrosive
nature. Moreover, the separation of catalysts from the product mixture involves more tedious
work-up after reaction is completed. Solid acid catalysts have the problem of rapid deactivation
due to coke formation. Though cation exchange resins showed good performance as catalysts,
they are thermally unstable and fouling of resin is a major issue.

Room temperature ionic liquids (RTILs) have growing potential applications as

environmentally benign alternative reaction media in organic transformations12-14. The
advantages of ionic liquids are lack of vapour pressure, wide range liquid, thermal stability and
recoverability15-16. Recently, tert-butylation of phenol has been reported using Lewis acidic ionic
liquids and yielded higher conversion, selectivity of 2,4-DTBP7,8. The major disadvantage of
these reported ionic liquid catalyzed reactions is decomposition of IL to form hydrofluoric acid.
________________________________________
*
Author for correspondence; E-mail: sreedevi@chemical.iitd.ac.in
Int. J. Chem. Sci.: 8(5), 2010 S579

In this present work, tert-butylation of phenol and p-cresol using Bronsted acidic functionalized
ionic liquid is reported which has no such disadvantages. The activity of ionic liquids is tested in
a batch reactor and recyclability of catalyst was checked.

EXPERIMENTAL
Material and methods
Materials and reagents

The experiments were conducted using the commercially available solvents and
chemicals and are used without further purification. Triethylamine, 1, 4-butane sultone, sulfuric
acid and solvent were supplied by M/s Sigma Aldrich Chemicals Pvt. Ltd, India. Phenol, p-
cresol and tert-butyl alcohol were supplied by Merck & CDH., New Delhi, India.
Preparation of ionic liquids

Sulfonic acid functional Bronsted acidic ionic liquids were prepared in the laboratory
following procedure in the literature17,18. Triethylamine was mixed with 1, 4-butane sultone by
stirring at 40-80C for 12-24 hours. After solidification, the zwitterions mass was washed with
ethyl ether and dried under a vacuum. Stoichiometric amount of sulfuric acid is added to the
zwitterions and the mixture was stirred at 80C for 8 hours to obtain ionic liquid. The structures
of the ionic liquids are presented in Scheme 1. (N-(4-sulfonic acid) butyl triethylammonium
hydrogen sulfate): 1H NMR (D2O, 400 MHz): (ppm) 1.1625 (t, 9H), 1.6599 (m, 4H), 2.5862
(t, 2H), 3.1376 (t, 2H), 3.1995 (m, 6H); 13C NMR (D2O, 100MHz): (ppm) 8.0002, 20.6977,
22.7652, 51.0469, 23.8737, 56.6530. Thermal decomposition of ionic liquid is observed at
325.4C.
SO3H
(CH3CH2)3N +
HSO4
(1-(4-Sulfonic acid) butyl triethylammonium hydrogen sulfate
Scheme 1: Structure of ionic liquids
Activity testing

The alkylation experiments were carried out in a sealed glass tube under autogeneous
pressure at given temperature. A typical batch contains 10 mmol each of phenol, tert-butyl
alcohol and ionic liquids. Reaction temperature was maintained at 70C and reaction mixture
was stirred around 800 rpm for 8 hours. At the end of the reaction, the mixture was cooled and
the products were extracted by toluene. A qualitative product analysis was conducted using a
GC-MS and quantitative analyses were conducted using NUCON GC which is supplied by
AIMIL India Ltd. using a CHROMSORB-WHP (2 m x 3.175 mm x 2 mm) column and flame
ionization detector.
S580 P. Elavarasan et al.: Synthesis of Antioxidants.

RESULTS AND DISCUSSION

Effect of reaction time on phenol conversion
Alkylation of phenol with tert-butyl alcohol is performed in a batch reactor under
autogeneous pressure at 70C. Fig. 2 shows the conversion of phenol using 1 : 1 molar ratio of
phenol to TBA and 1 : 1 molar ratio of phenol to IL.

100
90
Conversion & Selectivity 80
70
60
50 Conversion
ofphenol
40
Selectivity
30 of2TBP
20
10
0
0 100 200 300 400 500
Time (min)

Fig 1: Effect of reaction time on phenol conversion. Reaction condition : phenol (10 mmol):
TBA (20 mmol) : IL (1 : 1 : 2 IL : phenol : TBA) molar ratio at 70C

Alkylation of phenol with tert-butyl alcohol in the ionic liquid shows higher phenol
conversion and selectivity of 2-TBP (2-tert-butylphenol), 4-TBP (4-tert-butylphenol), 2, 4-
DTBP (2, 4-di-tert-butylphenol) and 2, 6-DTBP (2, 6-di-tert-butylphenol) products were
observed. Rapid conversion of phenol is observed with increased reaction time and selective
yield of 2, 4-DTBP reached a steady state after 8 hours. The maximum conversion of phenol was
achieved within first hour of reaction time. Initially, the selective yields to 2-TBP and 4-TBP
was high but as the reaction time increased, the selectivity to mono-alkylated (2-TBP and 4-TBP)
products decreased and the selectivity of 2, 4-DTBP increased owing to acidic nature of ionic
liquid. The conversion of phenol reached 84.5% and selectivity to 2, 4-DTBP reach 56.5%
respectively at a steady state. Scheme 2 gives the details of reaction mechanism, from the
mechanism the reaction are parallel and series.
Comparison of activity of the ionic liquid

The activity of prepared ionic liquids was compared in Table 1, with the earlier research
results obtained using solid and liquid acidic catalysts in the reaction. From the table, it is
evident that all three ionic liquids gave higher phenol conversion and good selectivity at low
temperature 70C. Also, good selectivity to 2, 4-DTBP (2, 4-di-tert-butylphenol) at the given
temperature is observed. The IL catalyst is also cost effective and less toxic18.
Int. J. Chem. Sci.: 8(5), 2010 S581

OH OH O

+ OH + H2O

Phenol tert-Butanol 2-tert-Butylphenol 4-tert-Butylphenol

OH OH OH OH

+ + OH + + H2O

tert-Butanol
2-tert-Butylphenol 4-tert-Butylphenol 2,4-Di-tert-butylphenol 2,6-Di-tert-butylphenol

Scheme 2: Reaction mechanism of tert-butylation of phenol in ionic liquid catalyst

Table 1: Activity of the various catalysts for alkylation of phenol with TBA

Molar ratio Conversion % Selectivity

Temp.
Catalyst TBA : 0 of phenol
C 2-TBP 4-TBP 2,4-DTBP 2,6-DTBP
phenol (%)
IL* 1:2 70 81.4 23.7 14.9 56.5 4.9
[bmim]PF6 7 1:2 60 90.3 13.8 10.9 75.3 -
[him]3 1:2 70 80.3 25.8 9.0 60.2 5.1
(CH2)4SO3]HSO46 10 : 6 80 20 2.8 97.2 - -
TPA/ZrO29 10 : 6 70 52.7 63.0 23.0 13.1 -
USY2 1:2 60 44.8 48.1 49.1 2.8 -
Mordenite9 10 : 6 70 44.8 29.0 49.0 21.2 -
TPA/Al-MCM-48 1:2 60 48.2 40.7 48.9 10.4 -
*Reaction conditions: phenol (10 mmol), ionic liquid (10 mmol); Speed = 800 rpm; Reaction time 8 h.

Effect of reaction time on p-cresol conversion

The influence of reaction time on conversion of p-cresol and the selectivity towards
TBC & DTBC was studied. Fig. 2 shows the conversion of p-cresol at 70C, 1 : 1 molar ratio of
p-cresol / TBA and 1 : 1 molar ratio of IL / p-cresol. The alkylation of p-cresol with TBA in the
ionic liquid gave a mixture of TBC, 2,6-di-tert-butyl-3-methyl phenol (2,6-DTBC) and
negligible amount (< 0.2%) of tert-butyl-p-cresol ether (TBCE). With increase in reaction time,
the conversion of p-cresol and selectivity to TBC and the yield of TBC increased rapidly and
reached an equilibrium level after 8 h and remain almost constant thereafter. In all the cases, it
was observed that 70.50 % of p-cresol conversion was achieved within the first hour of the
reaction time.
S582 P. Elavarasan et al.: Synthesis of Antioxidants.

80

70

60

% Conversion & Selectivity

50

40

30
Conversion of p-cresol

20
Selectivity of 2-TBC

10 Selectivity of 2,6-DTBC

0
0 100 200 Time min 300 400 500

Fig. 2: Effect of reaction time on p-cresol conversion. Reaction conditions: p-cresol (10 mmol),
TBA (20 mmol) and ionic liquid (10 mmol); Speed=800 rpm; Reaction time 8 h.

The conversion of p-cresol reached 65.7%, the selectivities to TBC and DTBC (BHT)
reached 66.4 % and 33.4 % respectively after 8 hours. The increase in the selectivity to TBC led
to decrease in selectivity to DTBC with time but the combined selectivities of TBC &DTBC
almost remains constant over the time period investigated. Reaction mechanism of tert-
butylation of p-cresol with tert-butyl alcohol using ionic liquid catalyst given in the scheme 3.
From experimental results there is no product formation of o-alkylated product, which gives the
improved product selectivity.
OH OH

+ OH + H2O

p-Cresol tert-Butanol 2-tert-Butyl-4-methylphenol

OH OH

+ OH + H2O

2-tert-Butyl-4-methylphenol tert-Butanol BHT

Scheme 3: Reaction mechanism of tert-butylation of p-cresol in ionic liquid catalyst

Recyclability of ionic liquid
In order to examine the recyclability of the ionic liquid, the ionic liquid was extracted
from the product mixture using toluene and dried under vacuum for 5 hr at 120C. After a
vacuum drying, the IL-1 is assessed with H-NMR spectroscopy, which showed no traces of
reactants or products. The results of the catalytic recycling experiment are shown in the Table 2.
IL was repeatedly used 5 times without major loss of phenol conversion and product selectivity.
Int. J. Chem. Sci.: 8(5), 2010 S583

Table 2: Recyclability of ionic liquids

Experimental run Conversion of phenol (%)* Conversion of p-cresol (%)$
Fresh catalysts 81.5 65.4
Recycle 1 80.3 64.9
Recycle 2 79.6 64.8
Recycle 3 82.6 65.2
Recycle 4 81.7 65.1
Recycle 5 80.9 64.6
Reaction conditions:* phenol l (10 mmol), TBA (20 mmol), IL (10 mmol) at 70C for 8h.
$
p-cresol (10 mmol), TBA (20 mmol), IL (10 mmol) at 70C for 8h.

CONCLUSION
Selective liquid phase tert-butylation of p-cresol and phenol with TBA in room
temperature ionic liquid catalyst has been systematically carried out. Catalysis in IL shows good
selective yields of TBC from p-cresol and 2, 4-DTBP from phenol alkylation reactions with tert-
butylalcohol respectively. The experimental results show that tert-butylation of phenol and p-
cresol with TBA in Brnsted acidic ILs, as a novel environmental benign and recyclable catalyst
system, shows promise. This alkylation reaction has several advantages: (i) Catalytic amount of
IL can achieve high aromatic conversion and selectivity to the desired products. (ii) The ILs can
be directly reused after extraction and drying. Thus, these Bronsted acidic ionic liquids prove to
be efficient catalysts for a continuous and economical process for the production of butylated
phenols.

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