U.S. patent application number 14/922358 was filed with the patent office on 2017-04-27 for process for producing hydroquinone and derivates.
The applicant listed for this patent is Chang Chun Plastics Co. Ltd.. Invention is credited to Yi Hung Chou, Chien Fu Huang.
Application Number | 20170113991 14/922358 |
Document ID | / |
Family ID | 58546376 |
Filed Date | 2017-04-27 |
United States Patent
Application |
20170113991 |
Kind Code |
A1 |
Huang; Chien Fu ; et
al. |
April 27, 2017 |
PROCESS FOR PRODUCING HYDROQUINONE AND DERIVATES
Abstract
The present disclosure relates to an improved, environmentally
friendly, process for producing compounds such as hydroquinone
(benzene-1,4-diol) and its derivatives. The process can be carried
out at ambient temperature and pressure using a recyclable copper
catalyst and recyclable intermediate materials. The process
generally entails reacting an aromatic compound such as benzene
with hydrogen peroxide in the present of a pure elemental copper
catalyst or a copper (I) salt catalyst to form oxidation product
such as benzoquinone, and reducing the compound to hydroquinone or
a hydroquinone derivative.
Inventors: |
Huang; Chien Fu; (Taipei,
TW) ; Chou; Yi Hung; (Taipei, TW) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Chang Chun Plastics Co. Ltd. |
Taipei |
|
TW |
|
|
Family ID: |
58546376 |
Appl. No.: |
14/922358 |
Filed: |
October 26, 2015 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C07C 45/28 20130101;
C07C 37/07 20130101; C07C 46/04 20130101; C07C 46/04 20130101; C07C
37/07 20130101; C07C 46/06 20130101; Y02P 20/584 20151101; C07C
46/04 20130101; C07C 46/04 20130101; C07C 50/04 20130101; C07C
39/08 20130101; C07C 50/24 20130101; C07C 39/245 20130101; C07C
50/02 20130101; C07C 37/60 20130101; C07C 37/07 20130101; C07C
37/60 20130101; C07C 39/04 20130101 |
International
Class: |
C07C 46/06 20060101
C07C046/06; C07C 37/60 20060101 C07C037/60; C07C 45/28 20060101
C07C045/28 |
Claims
1-9. (canceled)
10. A process for producing hydroquinone comprising reacting
benzene with hydrogen peroxide in the presence of elemental copper
catalyst or a copper(I) salt catalyst to form oxidation product
comprising benzoquinone and phenol, and converting the oxidation
product to hydroquinone by reduction, provided that the selectivity
for hydroquinone from benzene is greater than 60%.
11. The process according to claim 10, wherein the catalyst is a
copper(I) salt catalyst and the copper (I) salt catalyst is a
tetrakis(acetonitrile)copper(I) salt having the following formula:
Cu(CH.sub.3CN).sub.4-A, wherein A is an anion.
12. The process of claim 11, wherein the anion is selected from the
group consisting of ClO.sub.4.sup.-, NO.sub.3.sup.-,
BF.sub.4.sup.-, PF.sub.6.sup.-, and CF.sub.3SO.sub.3.sup.-.
13. (canceled)
14. The process of claim 10 carried out at a temperature of from
10.degree. C. to 80.degree. C.
15. The process of claim 10, wherein the reaction of benzene with
hydrogen peroxide is carried out in a solvent.
16. The process of claim 15, wherein the solvent is selected from
the group consisting of nitrile, a C.sub.3-C.sub.7 ketone, a
C.sub.5-C.sub.10 ether, a C.sub.2-C.sub.7 ester, and a
C.sub.5-C.sub.10 hydrocarbon.
17. The process of claim 16, wherein the nitrile is selected from
the group consisting of acetonitrile, propionitrile, butanenitrile,
and benzonitrile.
18. A process for producing hydroquinone comprising: (a) reacting
benzene with hydrogen peroxide in the presence of elemental copper
catalyst or a copper(I) salt catalyst dissolved in acetonitrile at
a temperature of between 10.degree. C. to 80.degree. C.; (b)
separating a water phase from an oil phase generated in (a); (c)
adding additional benzene and acetonitrile to the water phase and
using azeotropic distillation at a temperature of between
65.degree. C. to 90.degree. C. to remove the water and
acetonitrile; (d) regenerating the used catalyst in (a); (e)
separating the mixture of benzoquinone and phenol from the
unreacted benzene and acetonitrile; (f) recycling the unreacted
benzene and acetonitrile of (e) and using it as the additional
benzene and acetonitrile added to the water phase in (c); and (g)
converting the mixture of benzoquinone and phenol to hydroquinone
by reduction.
19. (canceled)
20. The process of claim 18, wherein a selectivity ratio for
hydroquinone is greater than about 2.
21. The process according to claim 10, wherein the catalyst is an
elemental copper catalyst.
22. The process according to claim 15, wherein the solvent
comprises acetonitrile.
23. A process for producing hydroquinone comprising: reacting
benzene with hydrogen peroxide in solvent in the presence of
elemental copper catalyst or a copper(I) salt catalyst to form
oxidation product comprising benzoquinone and phenol; removing
water generated by the reaction of benzene with hydrogen peroxide;
and converting the oxidation product to hydroquinone by reduction,
provided that the selectivity percent for hydroquinone from benzene
is greater than 60%.
24. The process according to claim 23, wherein the catalyst is a
copper(I) salt catalyst.
25. The process according to claim 23, wherein the copper (I) salt
catalyst is a tetrakis(acetonitrile)copper(I) salt having the
following formula: Cu(CH.sub.3CN).sub.4-A, wherein A is an
anion.
26. The process according to claim 23, wherein the catalyst is an
elemental copper catalyst.
27. The process according to claim 23 carried out at a temperature
of from 10.degree. C. to 80.degree. C.
28. The process according to claim 23, wherein the solvent is a
nitrile.
29. The process according to claim 23, wherein the nitrile is
acetonitrile.
30. The process according to claim 23, further comprising
regenerating the catalyst.
31. The process according to claim 23, further comprising recycling
unreacted benzene and solvent.
Description
FIELD OF THE DISCLOSURE
[0001] The present disclosure relates to an improved,
environmentally friendly, process for producing compounds such as
hydroquinone (benzene-1,4-diol) and its derivatives. The process
can be carried out at ambient temperature and pressure using a
recyclable copper catalyst and recyclable intermediate
materials.
BACKGROUND
[0002] Hydroquinone (or 1,4-dihydroxybenzene) has many uses. Many
of the uses are associated with hydroquinone's action as a reducing
agent that is soluble in water. For example, hydroquinone is used
as a developing agent in black-and-white photography, lithography,
and x-ray films. It is also used as an intermediate to produce
antioxidants for rubber and food. Furthermore, it is added to a
number of industrial monomers to inhibit polymerization during
shipping, storage, and processing. As a polymerization inhibitor,
hydroquinone prevents polymerization of acrylic acid, methyl
methacrylate, cyanoacrylate, and other monomers that are
susceptible to radical-initiated polymerization.
[0003] Hydroquinone can undergo mild oxidation to convert to the
compound parabenzoquinone, C.sub.6H.sub.4O.sub.2, often called
p-quinone or simply quinone. Reduction of quinone reverses this
reaction back to hydroquinone. Some biochemical compounds in nature
have this sort of hydroquinone or quinone section in their
structures, such as Coenzyme Q, and can undergo similar redox
interconversions.
[0004] In human medicine, hydroquinone is sometimes used topically
for skin whitening and/or to reduce the color of skin. Hydroquinone
is sometimes combined with alpha hydroxy acids that exfoliate the
skin to quicken the lightening process. There are several
disadvantages of existing hydroquinone manufacturing process, such
as low selectivity; highly polluted waste stream; high reaction
temperature and energy cost.
SUMMARY OF THE DISCLOSURE
[0005] The instant disclosure relates to a process for producing
hydroquinone and hydroquinone derivatives. The process is
particularly advantageous because it does not produce catechol,
which is a common by-product in the manufacture of hydroquinone.
Furthermore, the process uses hydrogen peroxide as the oxidant
resulting in the formation of water and oxygen, which are both
non-polluting compounds. The copper catalyst can be recycled and
re-used multiple times. Therefore, the process is environmentally
friendly. Finally, the process can be carried out at room
temperature and pressure, and therefore does not require huge
amounts of energy.
[0006] FIG. 1 illustrates three common mechanism that can be used
to manufacture hydroquinone: (1) analine oxidation; (2)
diisopropylbenzene (DIPB) oxidative cleavage; and (3) phenol
hydroxylation. See, e.g., FIG. 1. The advantages that the instant
process (inventive process) provides over these other three common
mechanisms are summarized in the following table.
TABLE-US-00001 Process Features Inventive Process Direct The
instant process be carried out continuously and Oxidation provides
for yields of at least 60% under mild reaction of Benzene
conditions, i.e., at room temperature and ambient According to
pressure. The byproduct phenol (B.P. 181.7.degree. C.) is easy the
Instant to separate and recycled. Also the catalyst can Disclosure
continually be regenerated and recycled. Thus, it is "clean" and
"environmentally friendly." Comparative Processes Aniline Although
this process can provide high yields, it Oxidation produces
substantial amounts of waste (Fe/Mn metal ions). Also this process
cannot be carried out continuously-it must be processed batch-wise.
These factors contribute to high cost. DIPB Although this process
is less costly than the analine Oxidative oxidation process (about
30% less costly than the aniline Cleavage process), it produces
impurities and low cost byproducts such as acetone. Phenol Although
this process uses hydrogen peroxide as the Hydroxylation oxidant,
which does not cause pollution, it has very low yields; less than
50%. It also produces Catechol (B.P. 245.5.degree. C.) as a
byproduct, which is difficult and costly to separate.
[0007] The instant process for producing hydroquinione and
hydroquinone derivatives (compounds of Formula (III)) generally
comprises:
(A) reacting a compound of Formula (I) with hydrogen peroxide in
the presence of elemental copper catalyst or a copper (I) salt
catalyst to form the oxidation product of Formula (II):
##STR00001##
[0008] wherein each X is independently a halogen, a C.sub.1-C.sub.8
alkyl, a C.sub.1-C.sub.8 alkenyl, a C.sub.1-C.sub.8 alkoxy, a
C.sub.3-C.sub.8 cycloalkyl, or a C.sub.6-C.sub.20 aryl group; each
Y is independently a carbonyl or a hydroxyl; n is an integer from 1
to 3; and m is an integer from 0 to 4; and
(B) converting the oxidation product of Formula (II) to a compound
of Formula (III) by reduction:
##STR00002##
[0009] The catalyst for reacting a compound of Formula (I) with
hydrogen peroxide can be an elemental copper catalyst or a copper
(I) salt catalyst, for example a tetrakis(acetonitrile) copper (I)
salt having the following formula: Cu(CH.sub.3CN.sub.4)-A, wherein
A is an anion. For example, the anion may be ClO.sub.4.sup.-,
NO.sub.3.sup.-, BF.sub.4.sup.-, PF.sub.6.sup.-, and
CF.sub.3SO.sub.3.sup.-.
[0010] The reaction of the compound of Formula (I) with hydrogen
peroxide is typically carried out in a solvent. The solvent may be,
for example, a nitrile, a C.sub.3-C.sub.7 ketone, a
C.sub.5-C.sub.10 ether, a C.sub.2-C.sub.7 ester, or a
C.sub.5-C.sub.10 hydrocarbon. Examples of a nitrile include, but
are not limited to, acetonitrile, propionitrile, butanenitrile, and
benzonitrile. In some cases, acetonitrile is used as the solvent in
the reaction of the compound of Formula (I) with hydrogen
peroxide.
[0011] The process can be specific for producing hydroquinone by
using benzene as the compound of Formula (I) and reacting it with
hydrogen peroxide in the presence of elemental copper catalyst or a
copper (I) salt catalyst to form benzoquinone and phenol, and
converting the benzoquinone to hydroquinone by reduction.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] Implementations of the present technology will now be
described, by way of example only, with reference to the attached
figures, wherein:
[0013] FIG. 1 is a diagram illustrating various methods that are
used to produce hydroquinone;
[0014] FIG. 2 is flow diagram illustrating an embodiment of the
instant disclosure;
[0015] FIG. 3 provides experimental results using
tetrakis(acetonitrile)copper (I) perchlorate as a catalyst; and
[0016] FIG. 4 provides experimental result using elemental copper
as a catalyst.
[0017] It should be understood that the various aspects are not
limited to the arrangements and instrumentality shown in the
drawings.
DETAILED DESCRIPTION OF THE DISCLOSURE
[0018] The process for producing hydroquinione and hydroquinone
derivatives (compounds of Formula (III)) generally comprises:
(A) reacting a compound of Formula (I) with hydrogen peroxide in
the presence of an elemental copper catalyst or a copper (I) salt
catalyst to form the oxidation product of Formula (II):
##STR00003##
[0019] wherein each X is independently a halogen, a C.sub.1-C.sub.8
alkyl, a C.sub.1-C.sub.8 alkenyl, a C.sub.1-C.sub.8 alkoxy, a
C.sub.3-C.sub.8 cycloalkyl, or a C.sub.6-C.sub.20 aryl group; each
Y is independently a carbonyl or a hydroxyl; n is an integer from 1
to 3; and m is an integer from 0 to 4; and
(B) converting the oxidation product of Formula (II) to a compound
of Formula (III) by reduction:
##STR00004##
[0020] The catalyst for reacting a compound of Formula (I) with
hydrogen peroxide can be an elemental copper catalyst or a copper
(I) salt catalyst, for example a tetrakis(acetonitrile) copper (I)
salt having the following formula: Cu(CH.sub.3CN.sub.4)-A, wherein
A is an anion. The anion may be, for example, ClO.sub.4.sup.-,
NO.sub.3.sup.-, BF.sub.4.sup.-, PF.sub.6.sup.-, and
CF.sub.3SO.sub.3.sup.-. Typically, Formula (II) results in a
mixture, wherein Y is hydroxyl on some compounds and carbonyl on
other compounds. Therefore, a mixture of compounds of Formula (II)
will often exist.
[0021] The reaction of the compound of Formula (I) with hydrogen
peroxide is typically carried out in a solvent. The solvent may be,
for example, a nitrile, a C.sub.3-C.sub.7 ketone, a
C.sub.5-C.sub.10 ether, a C.sub.2-C.sub.7 ester, or a
C.sub.5-C.sub.10 hydrocarbon. Examples of a nitrile include, but
are not limited to, acetonitrile, propionitrile, butanenitrile, and
benzonitrile. In some cases, acetonitrile is used.
[0022] The process can be carried out at room temperature and
pressure. Room temperature is typically about 20 to about
30.degree. C. (about 68 to about 86.degree. F. and room pressure is
typically about 1 atm. In some cases, the temperature can be from
about 10.degree. C. to about 80.degree. C.; from about 15.degree.
C. to about 60.degree. C., from about 15.degree. C. to about
50.degree. C., from about 15.degree. C. to about 40.degree. C.,
from about 15.degree. C. to about 30.degree. C., or from about
15.degree. C. to 23.degree. C., 24.degree. C., or 25.degree. C.
Also, the temperature may be from about 15.degree. C., 16.degree.
C., 17.degree. C., 18.degree. C., 19.degree. C., or 20.degree. C.
to about 23.degree. C., 24.degree. C., 25.degree. C., 26.degree.
C., 27.degree. C., 28.degree. C., 29.degree. C., or 30.degree.
C.
[0023] The process allows for a selectivity of the compound of
Formula (III) to be greater than about 60%. Nonetheless, the
selectivity of the compound of Formula (III) may be greater than
about 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, or 95%. The
process is particularly useful because the high selectivity (the
high yields) are attained without the formation of catechol.
Catechol is a by-product associated with the phenol hydroxylation
method of synthesizing hydroquinone.
[0024] In some cases, the selectivity ratio for the desired product
is at least about 2. The "selectivity ratio" is the ratio of the
desired product formed (in moles) to the undesired product formed
(in moles), i.e., moles of hydroquinone produces to the moles of
phenol produced. The selectivity ratio, however, is typically
higher than at least 2. For example, the selectivity ratio can be
at least about 3, about 4, about 5, about 6, about 7, about 8,
about 9, about 10, about 11, or higher. Often, the selectivity
ratio is in the range of from about 3 to about 12, about 5 to about
11, or about 8 to about 11.
[0025] The process can be specific for producing hydroquinine by
using benzene as the compound of Formula (I) and reacting it with
hydrogen peroxide in the presence of elemental copper catalyst or a
copper (I) salt catalyst to form benzoquinone and phenol, and
converting the benzoquinone to hydroquinone by reduction. For
instance, the process for producing hydroquinone may comprise:
[0026] (a) reacting benzene with hydrogen peroxide in the presence
of elemental copper catalyst or a copper (I) salt catalyst
dissolved in acetonitrile at a temperature of between 10.degree. C.
to 80.degree. C.;
[0027] (b) separating a water phase from an oil phase generated in
(a);
[0028] (c) using azeotropic distillation at a temperature of
between 65.degree. C. to 90.degree. C. to remove the water and
acetonitrile and optionally adding additional benzene and
acetonitrile to the water phase;
[0029] (d) regenerating the used catalyst in (a);
[0030] (e) separating the mixture of benzoquinone and phenol from
the unreacted benzene and acetonitrile;
[0031] (f) recycling the unreacted benzene and acetonitrile of (e)
and using it as the additional benzene and acetonitrile added to
the water phase in (c); and
[0032] (g) converting the mixture of benzoquinone and phenol to
hydroquinone by reduction.
[0033] One embodiment of the instant disclosure is represented in
FIG. 2, which is a flow diagram depicting various steps that can be
incorporated into the process. Examples of various steps that may
be included in the process include the following.
[0034] Oxidation of a Compound of Formula (I)
[0035] The oxidation of a compound of Formula (I) (e.g., benzene)
can be carried out at room temperature and atmospheric pressure in
a stirred reactor. A solvent, such as acetonitrile, can be used to
dissolve the catalyst. Such a solvent functions as a co-solvent for
benzene and hydrogen peroxide.
[0036] Water Removal
[0037] After carrying out the oxidation step described above, water
can be removed by any method known in the art.
[0038] Catalyst Regeneration
[0039] The copper catalyst can be regenerated and re-used. The
catalyst is regenerated by raising temperature above about
70.degree. C., and using copper to revert the copper (II) to copper
(I). Any un-reacted copper may be subsequently removed by
filtration. Also, a packed bed (a hollow tube, pipe, or other
vessel that is filled with a packing material, which is well-known
to those in the art) can be used in this step.
[0040] Solvent/Compound of Formula (I) Recycle
[0041] A distillation tower can be used to separate product and
un-reacted reactant (e.g., acetonitrile/benzene). The separated
reactant can purge to the azeotropic distillation tower and be used
as an entrainer.
[0042] Compound of Formula (II) Separation
[0043] By using extraction and distillation, the compound of
formula (II) (e.g., benzoquinone) can be separated from the other
materials and compounds produced (e.g., phenol).
[0044] Reduction of Compound of Formula (II)
[0045] The compound of formula (II) (e.g., benzoquinone) can be
transformed to a compound of formula (III) (e.g., hydroquinone) by
hydrogenation.
Example 1
(Synthesis of Hydroquinone with Tetrakis(acetonitrile)copper (I)
Perchlorate Catalyst)
[0046] 3.30 g of copper perchlorate catalyst was dissolved in 350 g
of acetonitrile (solvent). 197 g of benzene as added to the
mixture. Hydrogen peroxide (10%) was also added (17.2 g of
H.sub.2O.sub.2 and 155 g of H.sub.2O). The reaction temperature was
maintained at about 30.degree. C. for 12 hours. The
tetrakis(acetonitrile)copper (I) perchlorate catalyst was
regenerated after the reaction and the process repeated 19 times.
The results are graphically reported in FIG. 3.
[0047] FIG. 3 reports the grams of benzoquinone (BQ) produced per
gram of catalyst; grams of phenyl (PN) produced per gram of
catalyst; total grams of product produced per gram of catalyst; and
the selectivity ratio. Please note that the "selectivity ratio" is
the ratio of the desired product formed (in moles) to the undesired
product formed (in moles), i.e., moles of hydroquinone produces to
the moles of phenol produced. The table below presents the same
data provided in FIG. 3 except that the selectivity for the
hydroquinone is presented as a percentage of the total products
produced (i.e., hydroquinone and phenol). As shown in the table
below, in all cases the selectivity for hydroquinone was greater
than 60% and in many cases higher than even 90%.
TABLE-US-00002 Copper Perchlorate Catalyst Selectivity Ration
(moles Selectivity Percent (% of of hydroquinone to hydroquinone
compared to Run moles of phenol) total products produced) 0 3.27
78.8 1 1.50 63.3 2 3.82 81.4 3 2.86 76.8 4 2.60 75.0 5 8.09 90.2 6
9.22 91.5 7 10.16 92.0 8 9.11 91.2 9 9.18 91.2 10 11.08 92.7 11
11.07 92.7 12 11.08 92.6 13 10.55 92.5 14 10.26 92.1 15 4.73 84.4
16 9.53 91.6 17 10.99 92.8 18 10.32 92.3 19 10.13 92.0
Example 2
Synthesis of Hydroquinone with Pure Copper Catalyst
[0048] 3 g of pure copper catalyst (copper powder) was dissolved in
350 g of acetonitrile (solvent). 197 g of benzene was added to the
mixture. Hydrogen peroxide (10%) was also added (17.2 g of
H.sub.2O.sub.2 and 154.8 g of H.sub.2O). The reaction temperature
was maintained at about 30.degree. C. for 12 hours. The copper
catalyst was regenerated (2 g of copper powder) after the initial
reaction and the process repeated 8 times. The results are
graphically reported in FIG. 4.
[0049] FIG. 4 reports the grams of benzoquinone (BQ) produced per
gram of catalyst; grams of phenyl (PN) produced per gram of
catalyst; total grams of product produced per gram of catalyst; and
the selectivity ratio. Please note that the "selectivity ratio" is
the ratio of the desired product formed (in moles) to the undesired
product formed (in moles), i.e., moles of hydroquinone produces to
the moles of phenol produced. The table below presents the same
data provided in FIG. 4 except that the selectivity for the
hydroquinone is presented as a percentage of the total products
produced (i.e., hydroquinone and phenol). As shown in the table
below, in all cases the selectivity for hydroquinone was greater
than about 80%; and in all but one case, higher than even 90%.
TABLE-US-00003 Elemental Copper Catalyst (Copper Powder)
Selectivity Ratio (moles Selectivity Percent (% of of hydroquinone
to hydroquinone compared to Run moles of phenol) total products
produced) 0 9.72 91.7 1 3.47 79.9 2 9.43 91.5 3 10.66 92.5 4 9.93
91.9 5 9.52 91.6 6 9.83 91.9 7 10.19 92.2 8 9.53 91.6
Example 3
(Synthesis of 2-Methyl-1,4-Benzoquinone with
[Cu(MeCN).sub.4]ClO.sub.4 Catalyst)
[0050] 2-methyl-1,4-benzoquinone may be prepared by using 4.0 g of
[Cu(MeCN).sub.4]ClO.sub.4 catalyst dissolved in 350 g of
acetonitrile (solvent). 200 g of toluene is added to the mixture.
Hydrogen peroxide (10%) is also added (17.2 g of H.sub.2O.sub.2 and
155 grams of H.sub.2O). The reaction temperature is maintained at
about 30.degree. C. for 12 hours. The [Cu(MeCN).sub.4]ClO.sub.4
catalyst is regenerated after the reaction and the process is
repeated multiple times.
Example 4
Synthesis of 2,6-Dimethyl-1,4-Benzoquinone with Pure Copper
Catalyst
[0051] 2,6-dimethyl-1,4-benzoquinone may be prepared by using may
be prepared by using 3.0 g of pure copper catalyst (copper powder)
dissolved in 350 g of propionitrile (solvent). 200 g of m-xylene is
added to the mixture. Hydrogen peroxide (10%) is also added (17.2 g
of H.sub.2O.sub.2 and 155 grams of H.sub.2O). The reaction
temperature is maintained at about 30.degree. C. for 12 hours. The
copper catalyst is regenerated after the reaction and the process
is repeated multiple times.
Example 5
(Synthesis of 2-Tert-Butyl-1,4-Benzoquinone with
[Cu(MeCN).sub.4]NO.sub.3 Catalyst)
[0052] 2-tert-butyl-1,4-benzoquinone may be prepared by using may
be prepared by using 3.0 g of [Cu(MeCN).sub.4]NO.sub.3 catalyst
dissolved in 350 g of acetonitrile (solvent). 200 g of
tert-butylbenzene is added to the mixture. Hydrogen peroxide (10%)
is also added (17.2 g of H.sub.2O.sub.2 and 155 grams of H.sub.2O).
The reaction temperature is maintained at about 30.degree. C. for
12 hours. The [Cu(MeCN).sub.4]NO.sub.3 catalyst is regenerated
after the reaction and the process is repeated multiple times.
Example 6
(Synthesis of 2,6-Di-Tert-Butyl-1,4-Benzoquinone with
[Cu(MeCN).sub.4]BF.sub.4 Catalyst)
[0053] 2,6-di-tert-butyl-1,4-benzoquinone may be prepared by using
may be prepared by using 3.0 g of [Cu(MeCN).sub.4]BF.sub.4 catalyst
dissolved in 350 g of butanenitrile (solvent). 200 g of
1,3-di-tert-butylbenzene is added to the mixture. Hydrogen peroxide
(10%) is also added (17.2 g of H.sub.2O.sub.2 and 155 grams of
H.sub.2O). The reaction temperature is maintained at about
30.degree. C. for 12 hours. The [Cu(MeCN).sub.4]BF.sub.4 catalyst
is regenerated after the reaction and the process is repeated
multiple times.
Example 7
Synthesis of 2-Chloro-1,4-Benzoquinone with Pure Copper
Catalyst
[0054] 2-tert-butyl-1,4-benzoquinone may be prepared by using may
be prepared by using 3.0 g of pure copper catalyst (copper powder)
dissolved in 350 g of acetonitrile (solvent). 200 g of
chlorobenzene is added to the mixture. Hydrogen peroxide (10%) is
also added (17.2 g of H.sub.2O.sub.2 and 155 grams of H.sub.2O).
The reaction temperature is maintained at about 30.degree. C. for
12 hours. The pure copper catalyst is regenerated after the
reaction and the process is repeated multiple times.
[0055] The above embodiments are only used to illustrate the
principle of the present disclosure and the effect thereof, and
should not be construed as to limit the present disclosure. The
above embodiments can be modified and altered by those skilled in
the art, without departing from the spirit and scope of the present
disclosure. Therefore, the protection scope of the present
disclosure is defined in the following appended claims. As long as
it does not affect the effects and achievable goals of this
disclosure, it should be covered under the technical contents
disclosed herein.
[0056] The terms "comprising," "having," and "including" are used
in their open, non-limiting sense. The terms "a" and "the" are
understood to encompass the plural as well as the singular. The
expression "at least one" means one or more and thus includes
individual components as well as mixtures/combinations. The term
"about" when referring to a value, is meant specifically that a
measurement can be rounded to the value using a standard convention
for rounding numbers. For example, "about 1.5" is 1.45 to 1.54. All
valued set forth herein can be modified with the term "about" or
recited without the term, regardless of whether the term "about" is
specifically set forth (or is absent) in conjunction with any
particular value. All ranges and values disclosed herein are
inclusive and combinable. For examples, any value or point
described herein that falls within a range described herein can
serve as a minimum or maximum value to derive a sub-range, etc.
* * * * *