GB2080284A - Method of producing 4-(4- Hydroxyphenyl)-2-butanone - Google Patents
Method of producing 4-(4- Hydroxyphenyl)-2-butanone Download PDFInfo
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- GB2080284A GB2080284A GB8023874A GB8023874A GB2080284A GB 2080284 A GB2080284 A GB 2080284A GB 8023874 A GB8023874 A GB 8023874A GB 8023874 A GB8023874 A GB 8023874A GB 2080284 A GB2080284 A GB 2080284A
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- Prior art keywords
- butanone
- reaction
- hydroxyphenyl
- phenol
- hydroxy
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/70—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form
- C07C45/71—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form being hydroxy groups
Abstract
4-(4-Hydroxyphenyl)-2- butanone is produced by the reaction of phenol with 4-hydroxy-2-butanone in the presence of a cation exchange resin as catalyst. According to this method, the product is obtained with high percentage selectivity and in high yield; operational safety is enhanced; separation of resinous by-product from the main product is easy; and the reaction is easily controlled.
Description
SPECIFICATION
Method of producing 4 - (4 - hydroxyphenyl) - 2 butanone
This invention relates to a method of producing 4 (4- hydroxyphenyl) - 2 - butanone by reacting 4hydroxy - 2 - butanone with phenol. More particularly, it relates to an improvement according to which the range of reaction conditions of the reaction can be broadened and the product can be obtained with a higher yield.
For a method of producing 4 - (4 - hydroxyphenyl) 2 - butanone by reacting 4 - hydroxy - 2 - butanone with phenol, German Patent No. 2,145,308 discloses as catalyst the strong acid reagents having a pK in the range of -7 to +2.16, such as sulphuric acid, phosphoric acid, hydrogen chloride gas as well as p-toluenesulphonic acid. Further, Kogyo Kagaku
Zasshi (Japanese Chemical Industrial Magazine) Vol 57 (issue 1954), pages 4243, discloses as catalyst for the reaction the use of conc hydrochloric acid, conc sulphuric acid, potassium bisulphate, metallic sodium, aluminium chloride, or zinc chloride. When an acid or metallic sodium is used as the catalyst, the yield of the desired product 4 - (4 - hydroxyphenyl) 2 - butanone was considered as relatively high; nevertheless the yield is only about 45 to 62%.
Further, a resinous substance is produced as byproduct due to a side reaction, resulting in difficulty in the separation of 4 - (4 - hydroxyphenyl) - 2 butanone from the reaction mixture and in its subsequent purification. Furthermore, when using strong acids (including Lewis acids) as the catalyst, it is necessary to make the reactor highly corrosionresistant, and also after the reaction operations such as neutralization, washing, etc of the reaction mixture are required.
The present invention resides in a method of producing 4 - (4 - hydroxyphenyl) - 2 - butanone which is characterized by reacting 4 - hydroxy - 2 - butanone with phenol in the presence of a cation exchange resin as catalyst.
The present invention thereby enables one to minimize the above-mentioned drawbacks of the prior art, and provides a method of producing 4 - (4 - hydroxyphenyl) - 2 - butanone which can be operated with high selectivity and in high yield. In the present method, no strongly acidic, low molecular weight substances are used as the catalyst, thereby making it possible to use a reactor which is not highly corrosion-resistant and thus to enhance operational stability.
Moreover, it is now possible easily to separate the main product from any by-produced, resinous substance, and it is possible easilyto control the progress of the reaction.
Cation exchange resins which are employable as catalyst in the present invention are currently available commercially at a reasonable cost are those containing divinylbenzene; polymers constituting the skeleton of the substrate of such cation exchange resins are styrene-divinylbenzene copolymers or phenolformaldehyde resins. The percentage by weight of divinylbenzene contained in the cation exchange resins is usually expressed in terms of degree of crosslinking; those having degrees of crosslinking of 2 to 16 are commercially available.
Those having degrees of crosslinking of 2 or I less are inferior in the mechanical strengths against agitation or the like as well as the durability of ion exchangeability, whereas those having degrees of crosslinking of 12 or more show a weak catalyst activity.
As the cation exchange resins, those of the Natype are usually commercially available, but when they are used as the catalyst, it is necessary in advance of their use to convert the ion exchange group into a sulphone group, phosphoric acid group, sulphonamide group or the like group by means of sulphuric acid, phosphoric acid or the like. Further, in the case of cation exchange resins which are commercially available as the H-type, it is preferable from the point of exhibiting their function as catalyst to wash them with water thereby to bring them into a water-containing state, in advance of using them as catalyst.
As for the particle size of the cation exchange resins used in the present invention, those which make it possible to separate smoothly the liquid after the reaction from the cation exchange resins, ie.
those of about 20 to 200 mesh, are easy to use.
In the reaction of 4 - hydroxy - 2 - butanone with phenol, it is preferable to increase the molar ratio of phenol to 4 - hydroxy - 2 - butanone, eg. 3 to 10, thereby to minimize formation of any homopolymer of 4 - hydroxy - 2 - butanone, and thus to result in a superior percentage selectivity of reaction. When cation exchange resins are used for the first time as the catalyst for the method of the present invention, and in orderto permit their catalyst activity to be revealed, it is preferable to cause them to retain a water content of 5% by weight or higher, preferably about 10 to 20% by weight, for example by immersing them in advance in water.When the reaction of the present invention is repeated with the same catalyst, it is possible smoothly to carry out the reaction even when recovered cation exchange resins are again used as they are, since water has already been retained therein.
As for the apparatus for carrying out the reaction according to the method of the present invention a vessel reactor usually employed, having heating/cooling means and agitating means, should be sufficient. The respective amounts of phenol and a cation exchange resin can be fed to the vessel reactor, and 4 - hydroxy - 2 - butanone can then be added with stirring while the contents are heated or cooled.
Alternatively it is possible to add 4 - hydroxy - 2 butanone together with phenol and a cation exchange resin to the vessel reactor, and advance the reaction. With the reaction according to the method of the invention, it is also possible to carry it out continuously, employing an agitation reaction vessel as mentioned above or a packed column reaction apparatus.
When a cation exchange resin is used according to the method of the present invention, a resinous substance is by-produced (as in the case where conventional acid catalysts are used), but this substance has a smaller molecularweightthan that in the case of conventional catalysts and hence has fluidity; thus it
is possible easily to separate the resinous substance from the cation exchange resin coexistent therewith, eg, by centrifugal separation or the like means.
Whether the amount of cation exchange resin used is increased or decreased in the present invention, there is usually observed no disadvantageous effect upon the percentage selection of reaction rela tire to the object product.
The upper limit of the reaction temperature of the present invention is restricted by the heat-resistant temperatures of cation exchange resins, ie. usually 1200 to 1300C, though if the reaction temperature exceeds 90"C, the percentage selection of reaction is often somewhat reduced.On the other hand, for the lower limit of the reaction temperature, when 4 hydroxy 2 - butanone is added to and reacted with a mixture of phenol with a cation exchange resin in the absence of solvent, it is necessary to maintain the temperature at the time of initiation of the reaction at temperatures higher than 40"C, since the melting point of phenol is 42"C. If the reaction temperature is lower than 50"C, reduction in the reaction rate is observed, while normally no improvement in the percentage selection of reaction is observed.
In the reaction of the present invention, and even when the reaction temperature is varied during the reaction, there typically occurs neither reduction in the yield of 4 - (4 - hydroxyphenyl) - 2 - butanone nor rapid increase in the amount of resinous substance by-produced. On the other hand a rapid increase in the amount of resinous substance often occurs in the case of the conventional method employing acid catalysts. This fact indicates that according to the
method of the present invention, it is easy to control the reaction temperature to a suitable value.
In the method of the present invention, it is possible to use an inert solvent such as a lower aliphatic alcohol, or aromatic compound, eg. benzene.
The method of the present invention has advantages such as the following: (1) The percentage selectivity for phenol and 4 hydroxy - 2 - butanone relative to 4 - (4 - hydroxyphenyl) - 2 - butanone are high and the objective product is obtained with a high yield.
(2) It is possible to carry out the reaction with a reactor which is not highly corrosion-resistant (3) It is possible to carry out the operation with safety without using any strongly acidic catalyst.
(4) It is easy to separate from the objective product any resinous substance by-produced.
(5) It is easy to control the advance of the reaction (no rapid reaction occurs).
(6) Catalyst can be repeatedly used.
(7) Even if the reaction temperature is varied within a considerably broad range, the percentage selection and the yield are almost unchanged.
The present invention will be illustrated below by way of Examples.
Example 1
Phenol (reagent grade of first class) (282.3 g, 3.0 mols) and a cation exchange resin (Dowex-50Wx8, trademark of product manufactured by Dow Chemical Co., which is a H type prepared by sulphuric acid treatment; content of divinylbenzene, 8% by weight; water content, about 10% by weight) (100 g) were introduced into a 500 ml round bottom flask, and kept at 70"C with stirring, followed by adding 4 - hyd roxy-2-butanone (88.1 g, mol) over3 hours.
Thereafter agitation was continued at 700C for 12 hours until the extinct point 4 - hydroxy - 2 butanone was indicated by gas chromatography according to the internal standard method (this analytical method for liquid being applied to all of the subsequent ones). After completion of the reaction, the reaction mixture was taken out and analyzed. The amount of unreacted phenol was 1,112.4 g (2.0 mols)and that of4 - (4 - hydroxyphenyl) - 2- butanone formed was 112.4 9 (0.69 mol).
If the percentages selection of phenol and 4 - hydroxy - 2 - butanone, relative to 4 - (4 - hydroxyphenyl) - 2 - butanone formed are expressed by
number of mols of 4 - (4 - hydroxyphenyl) - 2
butanone formed4(number of mols of phenol fed) - (number of mols of unreacted phenol
recovered)} and
number of mols of 4 - (4 - hydroxyphenol) - 2
butanone formed/number of mols of4 - hydroxy
- 2 - butanone consumed, respectively,
then the percentages obtained were 70.7% and
68.4%, respectively.
The cation exchange resin in the reaction mixture
was separated by filtration, and the resulting reac
tion mixture after the separation was subjected to
simple distillation under a reduced pressure of 10
mmHg absolute at 150"C or lower. 95.2% of
unreacted phenol was recovered by the simple distil
lation, and 4 - (4 - hydroxyphenyl) - 2 - butanone in
the residue occupied 71.9% by weight thereof, the
remainder being a resinous substance having a
molecular weight of about 300 to 500 (as measured
by liquid chromatography). As for the amount of 4
(4 - hydroxyphenyl) - 2 - butanone, the amount
according to quantitative analysis of the reaction
mixture after the reaction accorded well with the
amount according to quantitative analysis of the
residue.
Example 2
The same starting raw materials and cation
exchange resin in the same amounts as in Example 1
were introduced together into a 500 ml round bot
tom flask and kept at 70"C with stirring to carry out
reaction for 15 hours until 4 - hydroxy - 2 - butanone
was extinct. As a result of analysis carried out as in
Example 1, the amount of unreacted phenol was
190.0 g (2.0 mols) and that of 4 - (4 - hydroxyphenyl) RK 2 - butanone formed as 110.7 g (0.68 mol). The percentages selection of phenol and 4 - hydroxy - 2- butanone were 68.7% and 67.4%, respectively.
This Example shows that even when the total
amounts of the starting raw materials and the catalyst are initially mixed together, the reaction can be
easily controlled without causing any rapid reaction.
Example 3
Example 1 was repeated except that the molar
ratio of phenol to 4 - hydroxy - 2 - butanone fed was varied by varying the amount of phenol alone, as shown in Table 1. The respective percentages selection of phenol and 4 - hydroxy - 2 - butanone meas
ured are shown in the Table Table 1
Molar ratio of \ 4-hydroxy-2 butanone 20 5.0 l 5-0 / 10.0 Percentage ion butanone 20 719 Phenol 60.2 71.9 723 | 4- Hydroxy - 2 - butanone | 58 | 72-6 74.1 Example 4
Example 1 was repeated except that the content of divinylbenzene (abbreviated to DVB) in the cationic
exchange resin was varied as shown in Table 2.The
respective percentages selection of phenol and 4 hydroxy - 2 - butanone measured are shown in the
Table.
As apparent from the Table, it is preferable for
avoiding breakage of the cationic exchange resin
that the content of DVB exceed 4% by weight, pref
erably 6% by weight.
Table 2
Percentage selection (%) Cation DVB content relative to Note exchange (% by relative 4-hydroxy resin weight to phenol 2-butanone DWX-50W x 2 2 68.5 67.6 Resin, broken OWX-50W x 4 4 69.8 68.0 Resin, broken OWX-50W x 6 69.3 68.4 DOWX-50W x 8 70.7 68.4 See Example 1 DOWX- 10 70.7 68.2 W x 10 OWX- 12 69.9 67.1 Reaction time, OW x 12 23 hrs.
DOWX- 16 69.3 65.9 Reaction time, 60W x 16 110 hrs.
Remarks: Reaction temperature, 70 C; reaction time of DOWX-50Wx2 ~
DOWX-50Wx10, 15 hours; and water content of cation exchange
resin, about 10% by weight.
Example 5
Example 1 was repeated except that the reaction temperature was varied as shown in Table 3 to
measure the reaction time (the time till 4 - hydroxy
2 - butanone was extinct).The results are shown in
Table 3.
Table 3
Percentage selection (%) Reaction Reaction relative to Note temperature time relative 4 - hydroxy - ( C) (hr) to phenol 2 - butanone 20 120 69.6 68.1 See Example2 42 50 69.5 68.5 70 15 70.7 68.4 See Example 1 90 7 68.2 67.8 120 3 62.9 63.3 Remarks: DOWX-50Wx8 was employed as cation exchange resin (water con
tent: about 10% by weight); reaction at 20 C was carried out as in
Example 2.
As apparent from the Table, even when the reac
tion temperature is varied in the reaction according
to the present invention, 4 - (4 - hydroxyphenyl) - 2
butanone is obtained with a high percentage selec
tion. It is also presumed indirectly from this fact that
even when the temperature is varied during the reac
tion, the percentage is high.
Example 6
Example 1 was repeated except that the same
cationic exchange resin as employed in Example 1 (DOWX50Wx8) was used 40 times. Although a por
tion of the cationic exchange resin was broken and
became fine, no change was observed in the reac
tion time and the percentage selection each time.
Example 7
Example 1 was repeated except that 200 g of thQ cation exchange resin were used. After reaction for
7.5 hours, analysis was carried out as In Example 1.
The amountsfreacted phenol and 4 - (4 - hyd-
roxyphenyl) - 2 - butanone formed were 191.0 g (2-0
mols) and 112.1 g (1.2 mol), respectively.
It is apparent from comparison of this Example
with Example 1 that the amount of the cation
exchange resin used, whether they are larger or
smaller, do not have so large an influence upon the
percentages selection of phenol and 4 - hydroxy - 2 butanone.
Comparative example 1
Sulfuric acid (98% by weight) was employed as
catalyst. Phenol (282.3g, 3.0 mols) and sulfuric acid
(7.4 9) were introduced into a 500 ml round bottom
flask and kept at 40 C with stirring. 4 - Hydroxy - 2
butanone (88.1 g, 1.0 mol) was then added over3
hours, followed by agitation at 40 C for additional 20
minutes. A 20% by weight NaOH aqueous solution
(30.2 g) was then added while the temperature was
kept at 40 C, to neutralize sulfuric acid. The resulting liquid after the reaction was analyzed by gas chromatography.As a result, the amounts of unreacted phenol and 4 - (4 - hydroxyphenyl) - 2 butanone formed were 186.4 g and 78.8 g (0.48 mol), respectively, and the percentages selection of phenol and 4 - hydroxy - 2 - butanone were 47.19/0 and 48.0%, respectively.
The reaction mixture after the neutralization was subjected to simple distillation under a reduced pressure of 10 mmHg at 1500C or lower. 94.3% of unreacted phenol was recovered by the simple distillation, and 4 - (4 - hydroxyphenyl) - 2 - butanone remained as residue, 4 - (4 - hydroxyphenyl) - 2 butanone occupied 51.7% by weight of the residue, and the remainder was resinous substance having a molecular weight of about 350 to 600 (according to liquid chromatography) and a small amount of - Na2SO4.
Comparative example 2
Phenol (282.3 B, 3.0 mols) and 4- hydroxy - 2 butanone (88.1 g, 1.0 mol) were introduced into a 500 ml round bottom flaskand kept at 20 C with stirring, and 7.4 g of sulfuric acid (98% by weight) were added at a time. The temperature inside the
reactor immediately rose up to 58 C to make temp- ~ eraturesontrol impossible. The reaction finished within a few minutes. Neutralization was then car
ried out as in Comparative example 1. As a result of
analysis according to gas chromatography, the
amounts of unreacted phenol and 4 - (4 - hydroxyphenyl) - 2 - butanone formed were 186.7 g (2.0
mols) and 77.5 g (0.47 mol), respectively.
it is apparent that the percentages selection of 4
(4 - hydroxyphenyl) - 2 - butanone obtained in Com
parative examples 1 and 2 were far lower than those
of Examples.
Claims (4)
1. A method of producing 4 - (4 - hydroxyphenyl) - 2 - butanone by reacting phenol with 4 - hydroxy - 2 - butanone, which comprises employing a cationic exchange resin as the catalyst for the reaction.
2. A method according to Claim 1, wherein the reaction is carried out at a temperature of 20 to 1200C.
3. A method according to Claim 1, wherein said
cation exchange resin has ion exchange groups
which are sulphone, phosphoric acid or sul
phonamide groups.
4. A method of producing 4 - (4 - hydroxyphenyl)
- 2 - butanone substantially as described herein in
the Examples.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8023874A GB2080284B (en) | 1980-07-22 | 1980-07-22 | Method of producing 4-(4-hydroxyphenyl)-2-butanone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8023874A GB2080284B (en) | 1980-07-22 | 1980-07-22 | Method of producing 4-(4-hydroxyphenyl)-2-butanone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2080284A true GB2080284A (en) | 1982-02-03 |
| GB2080284B GB2080284B (en) | 1984-06-20 |
Family
ID=10514930
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8023874A Expired GB2080284B (en) | 1980-07-22 | 1980-07-22 | Method of producing 4-(4-hydroxyphenyl)-2-butanone |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2080284B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1036455C (en) * | 1993-12-18 | 1997-11-19 | 江阴市顾山香料厂 | Synthesis of p-hydroxy-phenyl butanone |
| CN102372617A (en) * | 2011-11-09 | 2012-03-14 | 山东新和成药业有限公司 | Preparation method of spice 4-(4-hydroxyphenyl)-2-butanone |
| CN104355977A (en) * | 2014-11-06 | 2015-02-18 | 南京林业大学 | Synthesis process of raspberry ketone |
| CN104496778A (en) * | 2014-12-11 | 2015-04-08 | 南京林业大学 | Method for catalytic synthesis of raspberry ketone in presence of solid acid and alkali |
-
1980
- 1980-07-22 GB GB8023874A patent/GB2080284B/en not_active Expired
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1036455C (en) * | 1993-12-18 | 1997-11-19 | 江阴市顾山香料厂 | Synthesis of p-hydroxy-phenyl butanone |
| CN102372617A (en) * | 2011-11-09 | 2012-03-14 | 山东新和成药业有限公司 | Preparation method of spice 4-(4-hydroxyphenyl)-2-butanone |
| CN104355977A (en) * | 2014-11-06 | 2015-02-18 | 南京林业大学 | Synthesis process of raspberry ketone |
| CN104355977B (en) * | 2014-11-06 | 2016-03-02 | 南京林业大学 | A kind of synthesis technique of raspberry ketone |
| CN104496778A (en) * | 2014-12-11 | 2015-04-08 | 南京林业大学 | Method for catalytic synthesis of raspberry ketone in presence of solid acid and alkali |
| CN104496778B (en) * | 2014-12-11 | 2017-06-16 | 南京林业大学 | A kind of solid acid alkali catalytic synthesizes the method for raspberry ketone |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2080284B (en) | 1984-06-20 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PE20 | Patent expired after termination of 20 years |
Effective date: 20000721 |