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Indian Journal of Chemistry

Vol. 43B, June 2004, pp. 1349-1354

Note
hydroquinone (TMHQ) is one of the important raw
materials for synthesis of vitamin E . In the present
paper, a newly developed synthetic method is reported for TMHQ i.e. directly hydroxylation of 2, 3,
6-trimethylphenol with H 20 2 over copper hydroxyphosphate [Cu2(OH)P04] which has been used for
hydroxylation of phonel l -3 .
Many synthetic processes have been developed for
TMHQ.4-15 The typical examples are shown in
Scheme II and III, where the introduced substi tuents
X, Y and Y ' are not required for TMHQ itself. The
process becomes not only multi staged and complicated but also not favorable from the viewpoint of
environment, owing to the production of a lot of byproducts and pollutants. As mentioned above, all conventional methods producing TMHQ involves the
reduction of 2,3,6-trimethylbenzoquinone (TMBQ)
which is in general synthesized in multi-stages from
trimethylphenol (TMP). The new method developed
in this paper can produce TMHQ only in one step
from the starting material TMP which is commercially available, avoiding the use of multi-stages
processes.

A new process for the production of


trimethylhydroquinone
H Zhu* & S Y Chen
Institute of Catalysis, Zhejiang University (XiXi Campus)
Hangzhou 310028, P.R.China

Received 17 October 2002; accepted (revised) 8 December 2003


A new synthetic method for trimethylhydroquinone(TMHQ),
one of main feedstock for synthesis of vitamin E(VE), is reported .
All commercial processes for TMHQ is via 2, 3, 6-trimethylbenzoquinone and has disadvantages in their multi-steps and production of pollutants. To reduce the pollution and to decrease
synthesis steps, an attempt has been made to develop a si ngle-step
process for TMHQ, i.e. direct hydroxylation of 2, 3, 6-trimethylphenol (TMP) with H 20 2 over copper hydroxyphosphate
(CuiOH)P04) catalyst . The results show that the catalyst is of
high activity for hydroxylation of TMP and hi gh selectivity for
TMHQ. Some important factors affecting the catalytic activity
and selectivity have been studied. A green process for the production ofTMHQ cou ld be developed with deep study.
IPC: Int.Ct.1 C 07 C SO/OO

Vitamin E(a-tocopherol) has the structure shown in

Scheme I and has been widely used as a nutrient and


an antioxidant in the field of foodstuffs and animal
husbandry as well as medicine. The demand of vitamin E in the world is increasing rapidly. Natural vitamin E has been restricted in availability, so use of
synthetic vitamin E will increase rapidly. Trimethyl-

Experimental Section
Ethylenediamine (H 2NCH2CH2NH 2), phosphoric
acid (H3P04, 85 mass %), copper acetate (CuCH3COO),

OH
CH3
CH2=CH

HO

CH3
OH

CH3

C,sli3l

CH3

HO

CH3
CH 3

Scheme I-S ynthesis of vitamin E

INDIAN J. CHEM., SEC B, JUNE 2004

1350

CHAYCH'

Y
CH3

CH3

CH3

~xx---..

CH3

CH3

CH3

CH3

Y
Y

CH3

OR
CH3

H3

CH3

CH3

Y'

CH3

OR

X=S03H,Cl Br, i-Pr Y=N0 2,Cl Y'=NH 2


(I)

OH
CH3

OH
CH3

CH3

CH3

01-1

CY CH,
~;c
'" I CH,

dH

(2)
Scheme 11- Conventional method to produce TMHQ [(I), (2)]
OH

OH

--~

+
o
OH

Scheme III-New method to produce TMHQ

2,3,6 - trimethylphenol, and hydrogen peroxide (H20 2


30%) of analytical reagent were used.

Preparation of catalyst
The copper hydroxyphosphate was hydrothermally
synthesized. H2NCH2CH2 NH 2 , H 3 P04 , and CuAC 2
with molar ratio of 1.OH2 NCH 2CH 2NH2 : 2.9H3P04 :
1.0 CuCH 3COO : 25H20 according to the literature
procedure. The crystalline product was filtered,

washed with distilled water, and dried at ambient


temperature. The final deep green product with controlled crystal size was obtained.

Characterization
The samples in this work were characterized by Xray diffraction (XRD), scanning electron micrography
(SEM), differential thermal analysis (DT A), thermogravimetry analysis (TGA).

NOTES

Catalytic trim ethyl phenol hydroxylation


The hydroxylation of 2, 3, 6, -trimethylphenol was
performed in a 50 mL glass reactor and stirred with a
magnetic device. In a standard run, 7.3 mmol of
trimethylphenol, 2.5 mL of acetonitrile and 0.05 g of
catalyst were mixed in the reactor and heated to a
given temperature, followed by addition of 2.43 mmol
H20 2 (30% aqueous) (molar ratio of TMP/H 20 2=3.0).
After reaction for 4hr at SOC, the product were taken
out from the system and analyzed by gas chromatography(GC-9790, Flame Ionization Detector) with a
flexible quartz capillary column coated with SE-30.
The initial programmed temperature was at 130C,
the final temperature was at IS0C, and the injector
temperature was 2S0C.
Results and Discussion
Catalyst properties
There are several obvious peaks at 15.2, IS.5,
30.0, 34.2, and 37.3 in the range of 5-50 in XRD

1351

pattern (Figure 1) of synthesized copper hydroxyphosphate, which were assign to diffraction peaks of
CU2(OH)P04 crystallite I6 ,17.
In DTA curve of synthesized sample shown in
Figure 2, there is a peak of obvious weigh loss at
612C, which was assigned to dehydration of the
sample and could lead to a change in the sample
structure. The results indicate that CU2(OH)P04 is
thermally stable from 25 to 600C, and when the temperature was over 600C, the sample structure can
change to a new phase assigned to CU40(P04h
The particle size of the sample was estimated by
SEM measurement. The results indicate that the particle size is uniform and the crystal size could be controlled at 50-500llm by changing the synthesis conditions. The amount of N2 adsorption over CU2(OH)P04
catalyst is very low, and the BET surface area is only
1.2 m2/g, indicating that there were no micropore or
mesopore on it.

28

Figure l-XRD pattern of copper hydroxyphosphate

TG

o.
o.
00

1:

bIl

U
~

o.
t-

o.
'D

o.

.,.,

.,.o.o.
M

o.

o.

0::
0

o.

.I

100

200 300

400

500 600

700

800

Temperature CC)
Figure 2--The DT AffG curve of the as synthesized

INDIAN 1. CHEM., SEC B, JUNE 2004

1352

Catalytic hydroxylation of trimethylphenol

Figure 3. During 0-1.5 hr of reaction time the conver-

Catalytic activities and selectivity for 2, 3, 6trimethylphenol hydroxylation by H 20 2 at 353 Kover


various catalysts are presented in Table I. Na3P04 is
catalytically inactive. Ts-l is nearly none activity due
to its small pore size. Ti-MCM41 has very low activity in this reaction, which is familiar to its activity in
hydroxylation of phenol. However, CU2(OH)P04 is
catalytically active, giving conversion at 30.4%. Notably, although the surface area of this catalyst is
small (1.2 m2/g) and only the sites on the surface can
interact with reactants in catalysis, very high turnover
frequency (373 hOi) is achieved.
The effect of reaction temperature on hydroxylation of 2, 3, 6-trimethylphenol over CU2(OH)P04 catalyst is presented in Table II. The conversion increases
from 7.4 to 41.4% and the selectivity for trimethylhydroquinone decreases from 84.9 to 51.7 % when the
temperature goes up from 343 to 358 K. These results
are explained by the fact that trimethylhydroquinone
can be oxided into trimethylbenzoquinone with increasing temperature, which selectivity rises from 7.1
to 28.2%.
The dependence of TMP conversion and TMHQ
yield on reaction time for 2,3 ,6-trimethylphenol hydroxylation over CU2(OH)P04 catalyst is shown in

sion of TMP hydroxylation reaction (curve a) goes up


significantly, at 2 hr of reaction time the maximum
conversion is reached (curve b), TMHQ is major
product, relatively low by-products TMBQ and others
are formed. After 2 hr, the TMHQ yield decreases
slightly because of oxidation of TMHQ into TMBQ.
The concentration of H 20 2 has great influence on
the TMP conversion and the TMHQ selectivity. There
are two ways to change the concentration of H 20 2: (i)
change solvent amount or 2 (ii) change H20 2 amount.
Table III lists the dependence of catalytic activity
and selectivity on the concentration of H 20 2 over
CU2(OH)P04 catalyst. The conversion of 2,3,6trimethylphenol decreases and the selectivity for
trimethylhydroquinone increases with the amount of
solvent increase, but the selectivity for trimethylbenzoquinone decrease when the solvent amount is
changed from 2.5 to1O mL.
The different solvents were also used in thi s
reaction and their effect is shown in Table IV. When
acetone is used as solvent, the catalyst is nearly none
active; while in case of use of methanol and water, the
catalyst is active, TMP conversion is low. Acetonitrile
is the better solvent and water is best one among
studied solvents. The phenomenon is due to the

Table I-Activities and selectivity of 2,3,6-trimethylphenol hydroxyl ation over various catalysts by H 20 2"
Conv.(% )

Catalyst

Product selectivit,Y (%)b


Product 2

Product I
Na, P0 4
CU2(OH)P04
TS _lc

Others

30.4

82 . 1

8.7

9.1

3.6

79.8

9.9

10.2
4 .6

25.5
69.8
Ti-MCM-41
12.3
a: 2,3 , 6-trimethylphenoI1H 20 2=3(molar ratio) ; temperature: 353K,
solvent: 2.5 mL acetonitrile, reaction time: 2 hr.
b: Product I is trimethylhydroquinone, and Product 2 is trimethylbenzoquinone,
other is tar.
c: Cited from literature

Table 11- Effect of reaction temperature in 2,3.6-trimethylphenol hydroxylation with H 20 2 over copper
hydroxyphosphate [Cu2(OH)P04l"
Temperature (K)

Conv. (0/0)
Product 1
84.9
83 .8

Product selectivit,Y (%)b


Product 2
7.8
7.1

Others
7.3
8.9

343
348

7.4
16.8

353

30.4

82.1

8.7

9. 1

358

41.1

51.7

28.2

20.1

a: 2, 3, 6-trimethylphenoI1H 20 2=3 (molar ratio), solvent: 2.5 mL acetonitrile reaction time: 2hr
b: is defined as Table I

NOTES

1353

40
35

a
30

.__ .-- ----- ------------..- e

--------- ---------.------------

0-

''0"

:c
'>,
...0

25
20

CII

c:

15

10

...

'iii
c:

/ -/ -b
./

.~

0
0

0
0 .0

1 .0

0 .5

1 .5

2.0

2 .5

3.0

reaction tim e (h)


Figure 3- a: 2, 3, 6-Trimethylphenol conversion (mol% of theoretical conversion calculated on the basis of
2, 3, 6-trimethylphenol1H 20 2 molar ratio in the reaction system. b: product yields of trimethylhydroquinone.

Table 111- Effect of concentration of H20 2 in hydroxylation of 2, 3, 6-trimethylphenol with H20 2 over copper
hydroxyphosphate [Cu2COH)P041"
Product selectivity (%)b
Product I
Product 2

The amount of
solvent (ml)

The molar ratio of


reactant to H20 2

Conv.
(%)

2.5
5

3
3

30.4
24.2

82.1
83.7

8.7
7.7

9.1
9.6

7.5

15.6

84.9

7.5

7.5

others

10

12.5

89.0

6.4

4.61

2.5

28 .0

47.6

28 .8

23 .6

2.5

32.1

84.0

6.9

9.1

a: 2,3 , 6-trimethylphenoI1H 20 2=3 (molar ratio), solvent: 2.5 mL acetonitrile reaction time: 2 hr
b: is defined as Table I .

Table IV- Effect of solvents in hydroxylation of 2, 3, 6-trimethylphenol with H 20 2 over copper


hydroxylation Cu2COH)PO/
Solvent

Conv.( %)
Product 1

Acetone
Methanol
Water
Acetonitrile

3.3
20.8
17.8
30.4

Product selectivity (%l


Product 2

70.1
21.6
67.2
82.1

20.7
21.1
32.8
8.7

others
9.2
57.3
9.1

a: 2,3, 6-trimethylphenoI/H 20 2=3(molar ratio); temperature: 353K, reaction time: 2 hr.


b: is defined as Table I

polarity of solvent and dissolvability of solvent to


products.

showed that the process using trimethylphenol as a


starti ng material and consisting of one step is feasible.
It could be developed to a green process.

Conclusions
Copper hydroxyhosphate CU2(OH)P04 is an active
catalyst for the hydroxylation reaction of 2, 3, 6trimethylphenol to trimethylhydroquinone. The results

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