JPH0154332B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for decarbonylating organic acid halides. More specifically, the present invention relates to a method for decarbonylating organic acid halides using a novel decarbonylation catalyst. A method for partially or completely decarbonylating an organic acid halide using a catalyst to produce chlorine-substituted aromatic compounds, chlorine-substituted aliphatic compounds, etc. is known. For example, in partial or complete decarbonylation reactions of aromatic acid halides,
The use of platinum, palladium or nickel metals or compounds as catalysts is disclosed in GB 957,957. However, when using the decarbonylation catalyst as described above, the conversion rate is as low as about 50 to 75% under the conditions shown therein, which is not fully satisfactory industrially. In addition, the use of palladium or rhodium metals or compounds as catalysts in partial or complete decarbonylation reactions of aliphatic acid halides has been published by J.Amer.Chem.Soc., Journal of the American Chemical Society, 90 , 94 (1968). However, in this case, although the reaction progresses relatively easily, the conversion rate is about 70 to 90% under the conditions shown therein, which is not necessarily sufficient. As a result of various studies in search of highly active decarbonylation catalysts, the present inventors discovered that a catalyst containing a specific metal or a combination of metal compounds has a highly active catalytic action, which led to the completion of the present invention. . That is, in the decarbonylation reaction of an organic acid halide, the present invention comprises (a) at least one metal selected from palladium and rhodium or a compound of these metals and a carrier different from iron, cobalt, nickel, A method for removing organic acid halides characterized by using a catalyst comprising at least one compound selected from the group consisting of magnesium, zinc, copper, chromium, bismuth, molybdenum, platinum and gold supported on a carrier. This is a carbonylation method. The method of the present invention will be explained in more detail below. It is a constituent component of the catalyst in carrying out the method of the present invention.
As component (a), a metal and/or a metal compound of palladium and/or rhodium is used. Examples of the metal compound include chlorides, bromides, iodides, oxides, nitrates, sulfates, chlorinated metal acids, or salts thereof. Particularly preferred are chlorides, chlorinated metal acids, or salts thereof. The metal compound (b) that is one of the components of the catalyst includes beryllium, magnesium, boron, aluminum, cerium, neodymium, titanium, zirconium, hafnium, panadium, niobium, tantalum, chromium, molybdenum, and tungsten, which are different from the carrier. , manganese, rhenium, iron, cobalt, nickel, ruthenium, indium, platinum, gold, copper, zinc, cadmium, mercury, germanium, tin, antimony, bismuth, selenium, tellurium, and other metal halides, oxides, and sulfates. ,
Examples include nitrates, metal acids or salts thereof, chlorinated metal acids or salts thereof, and the like. Particularly preferred are iron, platinum, copper, bismuth, cobalt, nickel, chromium, gold halides, sulfates, nitrates, chlorinated metal acids, or salts thereof. Therefore, the decarbonylation activity of palladium or rhodium metal or metal compound alone is relatively low, but by combining it with component (b), which alone has almost no decarbonylation activity, The effect is that the decarbonylation activity is significantly increased compared to metals or compounds of palladium and/or rhodium. The weight ratio of component (a) and component (b) is generally 1:0.05 to 20, preferably 1:0.1 to 10. If the ratio of component (b) used in combination is less than 0.05, the combination effect will be slight, and even if it is 20 or more, the combination effect will be slight, which is not preferable. (a) The supporting ratio of component palladium and/or rhodium metal or its metal compound is per weight of the carrier.
It is preferably used in an amount of 0.1% by weight or more, particularly in the range of 0.2 to 5% by weight. If the loading rate of component (a) is less than 0.1% by weight, the activity will be low and productivity will decrease;
Furthermore, even if the amount supported is increased, no comparable effect can be obtained, so the amount supported is generally 10% by weight or less. The catalyst components (a) and (b) of the method of the present invention must be used in a state supported on a carrier, and the carrier may have a surface area of 1 m ² /g or more, preferably 10 m ² /g or more. Any carrier can be used, but commonly silica, alumina, activated carbon, diatomaceous earth, titania, zirconia, chromia, zinc oxide, silica alumina, silica titania, silica zirconia, alumina titania, alumina zirconia, silica chromia, alumina chromia Spheres, pellets, granules, or powders such as , titania chromia, etc. are used. Preferably, the carrier is alumina, silica,
Silica alumina, alumina titania, alumina zirconia, alumina chromia, silica titania,
Silica zirconia, silica chromia, etc. are used. A known method is used to prepare the catalyst, but generally the carrier is impregnated with a solution containing the palladium and/or rhodium compound (a), dried and reduced if necessary, and then the metal compound (b) is impregnated with a solution containing the palladium and/or rhodium compound. Components (a) and (b) are dissolved in a solvent, impregnated into a carrier, dried, and if necessary, component (a) is reduced to palladium or rhodium and fired. methods etc. are used. In carrying out the method of the present invention, the raw material organic acid halides include benzoyl chloride, benzoyl bromide, benzoyl iodide, phthalic acid chloride, phthalic acid bromide, phthalic acid iodide, isophthalic acid chloride, isophthalic acid bromide, isophthalic acid iodide, and terephthalic acid. Chloride, terephthalic acid bromide, terephthalic acid iodide, trimellitic acid chloride, trimellitic acid bromide, trimellitic acid iodide, hemimellitic acid chloride, hemimellitic acid bromide, hemimellitic acid iodide, trimesic acid chloride, trimesic acid bromide, trimesic acid iodide, prenitic acid chloride, Aromatic acid halides such as prenitic acid bromide, prenic acid iodide, pyromellitic acid chloride, pyromellitic acid bromide, pyromellitic acid iodide, and the above aromatic acid halides having substituents such as halogen, alkyl group, and nitro group, acetyl chloride, Acetyl bromide, acetyl iodide, propionic acid chloride, propionic acid bromide, propionic acid iodide, butyric acid chloride, butyric acid bromide, butyric acid iodide, valeric acid chloride, valeric acid bromide, valeric acid chloride, caproic acid chloride, caproic acid bromide, caproic acid Iodide, caprylic acid chloride, caprylic acid bromide, caprylic acid iodide, pelargonic acid chloride, pelargonic acid bromide, pelargonic acid iodide, capric acid chloride, capric acid chloride, lauric acid chloride, lauric acid bromide, lauric acid iodide, myristylic acid chloride, myristic acid bromide, myristic acid iodide, adipic acid chloride, adipic acid bromide, adipic acid iodide, pimelic acid chloride, pimelic acid bromide,
Aliphatic acid halides such as pimelic acid iodide, suberic acid chloride, suberic acid bromide, suberic acid iodide, sebacic acid chloride, sebacic acid bromide, sebacic acid iodide, and aliphatic acid halides having substituents such as halogenated alkyl groups , phenyl acetate chloride, phenyl acetate bromide, phenyl acetate iodide, phenylpropionic acid chloride, phenylpropionic acid bromide, phenylpropionic acid iodide, and other aliphatic acid halides having a phenyl group. In particular, the method of the present invention is effective for partial or complete decarbonylation reactions of aromatic acid halides. In carrying out the method of the present invention, the decarbonylation reaction can be carried out in either liquid phase or gas phase,
Further, the decarbonylation reaction temperature can be carried out at about 50 to 450°C, but this temperature is determined depending on the reactivity of the organic acid halide used as the raw material. In general, if the temperature is too high, the formation of by-products tends to increase significantly, while if the temperature is too low, the conversion rate will decrease. The temperature range is from the temperature at which the compound evaporates sufficiently to 450°C. The pressure is not particularly limited, and the reaction can be carried out either under reduced pressure, normal pressure, or increased pressure. After the completion of the reaction, tar-like residue is present on the catalyst, but most of the residue is removed by heating the reacted catalyst in air and reducing it if necessary. Since the heated catalyst has almost the same effect as a freshly prepared catalyst, the amount of catalyst used becomes extremely small when regeneration by heating the catalyst in air is considered. The method of the present invention described in detail above has industrial advantages in that the catalytic activity is higher than that of conventionally known catalysts, and the amount of organic acid halide reaction per catalyst is increased. The method of the present invention will be explained in more detail with reference to examples below, but the method of the present invention is not limited thereto. Example 1, Comparative Example 1 1.67 g of palladium chloride was dissolved in a hydrochloric acid aqueous solution of 4 ml of concentrated hydrochloric acid and 10 ml of water, and after diluting by adding 100 ml of water, a particle size of 3-4 mmφ and a specific surface area of 150 m ² /
The mixture was thoroughly mixed with 100 g of activated alumina, and dried with occasional stirring. Then, in a hydrogen stream
Reduction was carried out at 250°C for 6 hours. This is called catalyst A (for comparison). Take 10g of this catalyst A and 5% by weight of ferric chloride.
The mixture was thoroughly mixed with 10 g of an aqueous solution, dried with occasional stirring, and then dried in air at 400° C. for 4 hours. This is called catalyst B. Catalyst A is an alumina catalyst supporting 1% by weight of palladium, Catalyst B is an alumina catalyst supporting 1% by weight of palladium and dichloride.
It was an alumina catalyst supporting 5% by weight of iron. In order to see the electronegativity dependence, instead of the above ferric chloride, sodium chloride, calcium chloride,
Catalysts were similarly prepared using magnesium chloride, zinc chloride, copper chloride, chromium chloride or bismuth chloride. catalyze them respectively CDEFGHI
It is called. (Catalyst CD is for comparison) A catalyst was prepared in the same manner using a 5% by weight ethanol aqueous solution of molybdenum chloride instead of the 5% by weight aqueous solution of ferric chloride. This is called catalyst J. Table 1 summarizes these catalysts.

【table】

[Table] Next, fill a Pyrex glass tube with an inner diameter of 17 mmφ with 6 ml of the catalyst, heat it to 360°C, and then add 3 liters of nitrogen gas containing 30% by volume of isophthalic acid chloride.
The decarbonylation reaction was carried out for 2 hours by flowing contact at a rate of Hr. When the composition of the product consisting of organic compounds other than carbon monoxide obtained at the outlet of the reaction tube was analyzed, it was as shown in Table 2.

[Table] After the reaction, the catalyst was taken out and placed in air at 400℃ for 6 hours.
was heated to regenerate it into a metal oxide catalyst. After regeneration, the above reaction was carried out again, and the catalyst performance was almost the same as shown in Table 2. Example 2, Comparative Example 2 50 g of caprylic acid bromide and 4 g of each catalyst were added to a 100 ml round bottom flask equipped with a stirrer, and heated at 200°C.
The decarbonylation reaction was carried out for 5 hours by heating to a temperature of . The catalyst shown in Example 1 was used by crushing it with a mortar. The composition of the organic acid product obtained after the reaction was analyzed and was as shown in Table 3.

[Table] Example 3, Comparative Example 3 50 g of phenyl acetate chloride and 50 g of catalyst B from Reference Example 1 were added to a 100 ml round bottom flask equipped with a stirrer, heated to 250°C, and decarbonylated for 4 hours. After that, the composition of the product was as shown in Table 4. Similar experiments were conducted for catalysts B and G of Example 1. The results are shown in Table 4.

[Table] Example 4, Comparative Example 4 Dissolve 5.16 g of rhodium chloride trihydrate in a hydrochloric acid aqueous solution of 6 ml of concentrated hydrochloric acid and 16 ml of water, and then add 130 ml of water.
After adding and diluting, the particle size is 3 to 4 mmφ and the specific surface area is
Mix well with 210 m ² /g of silica alumina support,
The mixture was allowed to dry while stirring occasionally. Thereafter, reduction was carried out at 300° C. for 4 hours in a hydrogen stream.
This is called catalyst K (for comparison). 10 g of catalyst K was taken and thoroughly mixed with 10 ml of a 1.2% by weight aqueous solution of chloroplatinic acid, dried with occasional stirring, and then dried in air at 300° C. for 4 hours. This is called catalyst L. A catalyst was similarly prepared using 10 g of a 1% by weight aqueous solution of chloroauric acid instead of the 1.2% by weight aqueous solution of chloroplatinic acid. This is called catalyst M.

[Table] Next, 6 ml of the catalyst prepared as described above was filled in the same reaction tube as in Example 1, heated to 360°C, and nitrogen gas containing 30% by volume of 5-chloroisophthalic acid chloride was added at a rate of 3 liters/h. The decarbonylation reaction was carried out for 2 hours by flowing contact at high speed. When the composition of the product consisting of organic compounds other than carbon monoxide obtained at the outlet of the reaction tube was analyzed, it was as shown in Table 6.

[Table] Example 5 10 g of catalyst A was thoroughly mixed with 10 g of a 5% by weight solution of ferrous sulfate, dried with occasional stirring, and then dried in air at 400° C. for 4 hours. This catalyst is called catalyst N. A catalyst was prepared in the same manner as above except that ferric nitrate was used instead of ferrous sulfate. This catalyst is called catalyst O. A reaction similar to Example 4 was carried out using catalyst N or O. The results are shown in Table 7.

[Table] Example 6, Comparative Example 5 10 g of catalyst A and 10 g of 0.03, 0.5, 2, and 10% by weight aqueous solution of ferric chloride were mixed well, and dried with occasional stirring, and then heated at 400°C in air.
Drying was carried out for 4 hours. These are called catalysts P, Q, R, and S, respectively. These catalysts are palladium, ferric chloride, and alumina catalysts carrying 0.03, 0.5, 2, and 10% by weight of ferric chloride, respectively. Next, using catalyst P, Q, R or S, Example 1
The decarbonylation reaction was carried out in the same manner as above. The results are shown in Table 8.

[Table] Example 7 24.8 g of nickel nitrate hexahydrate was dissolved in 150 ml of water, mixed well with 95 g of activated alumina with a particle size of 40 mmφ and a specific surface area of 300 m ² /g, and evaporated to dryness while stirring occasionally. . Thereafter, it was fired in air at 500°C for 6 hours. After firing, 50 g of this was taken, immersed in 50 g of a hydrochloric acid solution containing 0.83 g of palladium chloride, and evaporated to dryness while thoroughly stirring and mixing. Thereafter, reduction was carried out at 400°C for 6 hours in a hydrogen stream. This is catalyst T
It is called. A reaction similar to that in Example 1 was carried out using Catalyst T. The results are shown in Table 9.

[Table] Comparative Example 6 After dissolving 5 g of ferric chloride in 100 ml of water, activated alumina with a particle size of 3 to 4 mmφ and a specific surface area of 150 m ² /g was prepared.
The mixture was thoroughly mixed with 100 g and dried with occasional stirring, and then dried in air at 400° C. for 4 hours. This is called catalyst U. Catalysts were prepared in the same manner using magnesium chloride, zinc chloride, copper chloride, chromium chloride, and bismuth chloride instead of the ferric chloride. These are called catalysts V, W, X, Y, and Z, respectively.

【table】

[Table] Decarbonylation was carried out by the same method as in Example 1. The results are shown in Table 11.

[Table] Example 8 After dissolving 3.37 g of rhodium nitrate dihydrate in 100 ml of water, it was thoroughly mixed with 100 g of alumina titania having a particle diameter of 4 mmφ and a specific surface area of 100 m ² /g, and was dried with occasional stirring. then 200 in air stream
Drying was carried out at ℃ for 4 hours. Take 10g of the dried catalyst, mix well with 20g of a 4% by weight aqueous solution of cupric chloride, dry with occasional stirring, and then heat in air at 400°C for 6
Time firing was performed. This is called a catalyst. The catalyst was an alumina titania catalyst supporting 3% by weight of rhodium nitrate and 8% by weight of cupric chloride. Separately, add 2.17 g of palladium chloride to 4 ml of concentrated hydrochloric acid.
Dissolve 10ml of water in a hydrochloric acid aqueous solution and add 100ml of water.
After adding ml and diluting, the particle size is 4mmφ and the specific surface area is 100.
Mix well with 100g of alumina zirconia of m ² /g,
The mixture was allowed to dry while stirring occasionally. Thereafter, it was dried for 4 hours at 200° C. in an air stream. Take 10g of the dried catalyst, mix well with 20g of a 3% by weight aqueous solution of cobalt bromide, dry with occasional stirring, and then heat in air at 500°C for 6
Time firing was performed. This is called a catalyst. The catalyst was an alumina zirconia catalyst supporting 1.5% by weight of palladium oxide and 6% by weight of cobalt chloride. Calcination temperature in catalyst preparation method
A catalyst was prepared in the same manner as Matsutaku except that the temperature was changed to 200°C. The obtained catalyst is called a catalyst. The catalyst was an alumina, zirconia catalyst supporting 2.2% by weight of palladium chloride and 6% by weight of cobalt chloride. Next, 6 ml of the catalyst prepared as above was filled into a Pyrex glass tube with an inner diameter of 17 mmφ, and the temperature was increased to 360°C.
After heating parachlorobenzoyl chloride to
Nitrogen gas containing 20% by volume was brought into contact by flowing at a rate of 3/H, and the decarbonylation reaction was carried out for 2 hours.
When the composition of the product consisting of organic compounds other than carbon monoxide obtained at the outlet of the reaction tube was analyzed, it was as shown in Table 12.

【table】

Claims (1)

[Scope of Claims] 1. In the decarbonylation reaction of an organic acid halide, (a) at least one metal selected from palladium and rhodium or a compound of these metals, and (b) iron, cobalt, nickel, Magnesium, zinc, copper, chromium, bismuth, molybdenum,
A method for decarbonylating organic acid halides, which comprises using a catalyst comprising at least one of platinum, gold halides, sulfates, nitrates, chlorinated metal acids, or salts thereof supported on a matrix. 2 The combined ratio of component (a) and component (b) is 1:
0.05-20. The method for decarbonylating an organic acid halide according to claim 1. 3 Supporting rate of catalyst component (a) is 0.1% by weight per carrier
The method for decarbonylating an organic acid halide according to claim 1 or 2, which is the above. 4. Claims 1, 2, or 3, wherein component (a) is palladium, rhodium, palladium, or a chloride, bromide, iodide, oxide, nitrate, sulfate, chloride metal acid, or a salt thereof. A method for decarbonylating organic acid halides.