Claims
- 1. A process for the preparation of a haloacetophenone of the formula ##SPC1## wherein X is chloro or bromo and n is 1-3, the halo substituents being meta and/or para to the ##EQU1## group, said process comprising oxidizing a halocumene of the formula: ##SPC2##
- wherein X and n are as defined above at a temperature between 130.degree.C. and 160.degree.C. with air or oxygen, and in the presence of a catalytically effective amount of a metal phthalocyanine selected from the group consisting of iron, copper and cobalt phthalocyanine and in the presence of a dichlorobenzene as a solvent.
- 2. The process of claim 1, wherein said metal phthalocyanine is copper phthalocyanine.
- 3. The process of claim 1, wherein oxidation is effected at a pressure between 0.2 and 50 atm.
- 4. The process of claim 1, wherein n is 1 and the halo substituents are para to the keto group.
- 5. The process of claim 1, wherein the halocumene and the dichlorobenzene are present in a weight ratio of about 0.5 to 1.0.
- 6. The process of claim 1, wherein the dichlorobenzene is o-dichlorobenzene.
- 7. The process of claim 1, wherein the amount of catalyst is about 0.1% by weight based on the halocumene.
- 8. The process of claim 1, wherein the reaction is run for from about 2 to 4 hours.
Priority Claims (1)
| Number |
Date |
Country |
Kind |
| 38629 |
Jan 1972 |
IL |
|
CROSS REFERENCE TO RELATED APPLICATIONS
This is a continuation-in-part of co-pending application, Ser. No. 317,590, filed on Dec. 22, 1972 now abandoned.
1. Field of the Invention
The invention relates to catalytic oxidation processes, and in particular, to such processes for producing haloacetophenones from the corresponding halocumenes while simultaneously minimizing the co-production of the corresponding halocarbinol which is an undesirable side product.
2. Prior Art
It is known that acetophenone and substituted acetophenones may be obtained by the liquid-phase oxidation of the respective ethylbenzenes. The rate of oxidation in this method, is however, slow, and undesirable by-products are obtained.
The liquid-phase oxidation of cumene (isopropylbenzene) by means of air or oxygen is also well known. When this process is effected in the absence of a catalyst, and at temperatures around 100.degree.C, cumene hydroperoxide is produced. When this process is effected in the presence of catalysts, such as transition metal salts, and, in particular, certain salts of cobalt, a mixture of acetophenone and methylphenyl carbinol in a mole ratio of about 1:1 is obtained. A similar molar ratio of products is obtained by the oxidation of halogen-substituted cumenes. The presence of large amounts of the obtained carbinol as a by-product is undesirable, because the need to either separate the products or convert the carbinol to the acetophenone adversely affects the economy of the process.
In U.S. Pat. No. 2,954,405, there is disclosed a process for the catalytic autooxidation of cumenes to produce the corresponding cumene hydroperoxide. These hydroperoxides, which are intermediates for the preparation of phenols are desirable products and accordingly, the maximizing of the yield of the hydroperoxide is of major significance in this patent. Of course, the simultaneous minimizing of the yield of the corresponding acetophenone is also desired.
In U.S. Pat. No. 2,291,915 there is disclosed a process for the preparation of styrenes by oxidizing a cumene in the absence or presence of a catalyst. This oxidation produces an approximately 1:1 mixture of the corresponding acetophenone and carbinol which is then subjected to further treatment to convert them to the desired styrene. When the cumene is oxidized in highly basic media, the carbinol is the main reaction product.
In none of this prior art is there any suggestion that the oxidation of a cumene can be so effected as to maximize the yield of the acetophenone and simultaneously minimize the yield of the carbinol (and the hydroperoxide).
An object of the present invention is to provide a novel process for the production of halo-substituted acetophenone derivatives.
In accordance with that object, it has now been found that the oxidation of halocumenes can be conducted in a manner which leads to the preferential production of the corresponding haloacetophenones with a simultaneous reduction in the relative amount of the corresponding halocarbinols, the latter being undesirable side products.
In particular, it has been found that when the air (or oxygen) oxidation of halocumenes is effected at temperatures between 50.degree. and 200.degree.C, preferably, between 130.degree. and 160.degree.C, with the use of a metal phthalocyanine catalyst, and most preferably, in the co-presence of an inert solvent such as a dichlorobenzene, the oxidation product principally comprises the desired haloacetophenone with relatively small amounts of the undesired corresponding halocarbinol. In its most preferred embodiment, the invention provides a process wherein the ratio of the haloacetophenone to the halocarbinol in the oxidation product is 16:1 as compared with the known processes wherein this ratio is generally about 1:1.
In accordance with the process of the present invention, the overall molar yield of the haloacetophenones with respect to the halocumene starting material is well over 90%.
The process according to the invention comprises oxidizing a halo-substituted cumene in the liquid phase by means of air or oxygen at a temperature in the range of between 50.degree. and 200.degree.C, preferably between 130.degree. and 160.degree.C, at a pressure of 0.2-50 atm., preferably 1-10 atm. in the presence of a catalytic amount of a metal phthalocyanine complex, generally, about 0.1% by weight of the halocumene, whereby about 30-90% of the starting halocumene is converted to the corresponding haloacetophenone. The haloacetophenone constitutes the major product of the oxidation reaction, with the corresponding halocarbinol being produced in lesser quantities along with minor amounts of formaldehyde.
The molar ratio of the haloacetophenone to the halocarbinol in the oxidation product is a function of the duration of the reaction. By extending the reaction for prolonged periods, i.e., to about 2-4 hours, this ratio increases as the proportion of halocarbinol approaches zero.
The metal phthalocyanines which may be used in the process include copper, cobalt and iron phthalocyanines.
In its most preferred embodiment, the process of the invention comprises running the above described oxidation in the copresence of an inert solvent such as a dichlorobenzene, preferably, o-dichlorobenzene. Under these conditions, the highest conversion of the starting halocumene is achieved, with the ratio of the produced haloacetophenone to halocarbinol being at its highest. The separation of the unreacted halocumenes and the by-product halocarbinol from the haloacetophenone is effected using conventional separation techniques.
US Referenced Citations (5)
Continuation in Parts (1)
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Number |
Date |
Country |
| Parent |
317590 |
Dec 1972 |
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Patent Grant
3954876
