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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.
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
1350
CHAYCH'
Y
CH3
CH3
CH3
~xx---..
CH3
CH3
CH3
CH3
Y
Y
CH3
OR
CH3
H3
CH3
CH3
Y'
CH3
OR
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
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,
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
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
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
1352
Table I-Activities and selectivity of 2,3,6-trimethylphenol hydroxyl ation over various catalysts by H 20 2"
Conv.(% )
Catalyst
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
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
--------- ---------.------------
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
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)
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 .
Conv.( %)
Product 1
Acetone
Methanol
Water
Acetonitrile
3.3
20.8
17.8
30.4
70.1
21.6
67.2
82.1
20.7
21.1
32.8
8.7
others
9.2
57.3
9.1
Conclusions
Copper hydroxyhosphate CU2(OH)P04 is an active
catalyst for the hydroxylation reaction of 2, 3, 6trimethylphenol to trimethylhydroquinone. The results
Reference
1 Xiao F S, Sun J M & Yu R, Studies in Surface and Catalysis,
130, 2000, 791.
2 Xiao F S, Sun J M & Xiang J M, Appl Catal A, 207, 2001 , 267.
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