JPH0674230B2 - Process for producing aromatic ketone - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing an aromatic ketone from an aromatic iodine compound, carbon monoxide and an aromatic compound.

[Conventional technology]

Various methods for producing aromatic ketones using carbon monoxide as one raw material are known. For example, the reaction of Grignard reagents such as phenylmagnesium bromide with carbon monoxide in the presence of a chromium chloride catalyst (Osaka University Faculty of Engineering report,
(Vol. 16, p. 205, 1966), Reaction of Grignard reagent with carbon monoxide and aromatic bromide in the presence of nickel complex catalyst (Chemical Society of Japan, p. 310, 1982), in the presence of cobalt carbonyl catalyst. Reaction of Organic Mercury Compounds with Carbon Monoxide (US Pat. No. 3,692,652), Reaction with Organic Mercury Compounds in the Presence of Palladium or Rhodium Catalysts [Journal of American Chemical Society]
(J.Amer.Chem.Soc.), 90, 5546, 1968; The Journal of Organic Chemistry (J.Org.C.
hem.), 45, 3840, 1980], reaction of an organotin compound with carbon monoxide and an aromatic halide in the presence of a palladium complex catalyst or a nickel complex catalyst (JP-A-56-292).
5; JP-A-57-59818), the reaction of phenyllithium with carbon monoxide at -70 ° C (Journal of
The American Chemical Society (J.Amer.Che
m.Soc.)), Vol. 95, p. 8118, 1973), using organometallic compounds such as organomagnesium halides, organomercury compounds, organotin compounds and organolithium compounds as other raw materials. There is. However, these methods generally require preparation of an organometallic compound which is unstable and cumbersome to handle, and these are inevitably expensive raw materials, and the yield and selectivity of aromatic ketones are high. Since it is not so high, there was a problem in industrial implementation. Further, a method of reacting a diaryliodonium salt with carbon monoxide and zinc in the presence of a palladium or rhodium catalyst (Journal of the Chemical Society of Japan, p. 585, 198).
4 years; JP-A-59-175447) is also known, but it requires complicated steps to prepare a diaryliodonium salt, and the yield and selectivity of aromatic ketone are 30 to 68%. Since it is low, there is a problem in implementing it industrially. Also,
Method for producing an aromatic-aliphatic asymmetric ketone by reacting an aromatic iodine compound with an aliphatic halide, carbon monoxide and an active zinc compound in the presence of a palladium catalyst (tetrahedron letter (Tetrahedron Letters
s), Vol. 24, p. 3869, 1983], but an active zinc compound such as zinc-copper couple is required in an equimolar amount or more, and an aromatic ketone such as benzophenone cannot be obtained.

Further, various methods are known in which a metal carbonyl compound is used as a raw material instead of carbon monoxide. For example, reaction of an organolithium compound with nickel carbonyl (Bull. Chem. Soc. Japan), Vol. 38, page 330, 1965.
, Organolithium compounds with iron carbonyls [Bullet of the Chemical Society of Japan (Bull.Chem.Soc.Japan), 37, 341, 1964]
Reaction of organic mercury compounds with cobalt carbonyl [J.Amer.Chem.Soc.], 90, 540, 1968.
Y .; ibid., 91, p. 3037, 1969], etc., a method of using an organometallic compound as another raw material, or a reaction between an aromatic diazonium salt and nickel carbonyl [Jearnal.
Of Chemical Society (J. Chem. Soc.), P. 686,
1962], but all of them use organic metal compounds and metal carbonyls, which are cumbersome to handle, as raw materials, and there are many problems in industrial implementation. Also known is a method of synthesizing an aromatic ketone by reacting an aromatic iodine compound with a metal carbonyl. For example, the reaction of iodobenzene with iron dodecacarbonyl [Bretane of the
Chemical Society of Japan (Bull.Chem.S
oc.Japan), Vol. 41, p. 1417, 1968] and the reaction of nickel carbonyl with pentafluoroiodobenzene, which is a special aromatic iodine compound [The Journal of.
Organic Chemistry (J.Org.Chem), Volume 32, 12
15 pages, 1967], but the yield in each case is low.

On the other hand, 4,4 'which is one of the preferred target products of the present invention
-As a method for producing difluorobenzophenone, the following method has been proposed in addition to the method described above.

(1) Diazotization of 4,4'-diaminodiphenylmethane in anhydrous hydrogen fluoride or a concentrated aqueous solution of hydrogen fluoride, and then in the presence of nitrous acid, decomposition and fluorination of diazonium salt and conversion of methylene group to ketone group. Method for simultaneous oxidation of
54-132558).

(2) A method of subjecting 1,1-bis (4-fluorophenyl) -2,2,2-trichloroethanol to alkali treatment (Japanese Patent Laid-Open No. 57-58242).
-154139).

(3) A method of reacting 4,4'-dichlorobenzophenone with an alkali fluoride (JP-A-57-169441).

(4) A method of carrying out a Friedel-Crafts type reaction of 4-fluorobenzoyl chloride and fluorinated benzene in the presence of boron trifluoride in anhydrous hydrogen fluoride (JP-A-58-124731).
Issue).

(5) A method of oxidizing 1,1-bis (4-fluorophenyl) -2,2-dichloroethylene with nitric acid (JP-A-58-126829)
Issue).

However, these methods require the use of a large amount of anhydrous hydrogen fluoride which is dangerous and difficult to handle (methods (1) and (4)) and diazonium fluoride which is unstable and has a risk of explosion. Must be produced (method (1)), complicated steps are required to produce the raw material compound (methods (2), (3), (5)), and must be reacted at high temperature for a long time Therefore, not only the side reaction increases and the yield does not increase so much, but it is difficult to separate the product from the raw material and the by-product (method (3)). There was a problem to implement.

[Object of the Invention]

Therefore, the present inventors have conducted earnest studies on a method for producing an aromatic ketone more inexpensively and more easily, and as a result, a new method for producing the target aromatic ketone with high yield and high selectivity. The present invention has been completed and the present invention has been completed.

[Structure of Invention]

That is, in the present invention, when an aromatic ketone is produced from an aromatic iodine compound, carbon monoxide and an aromatic compound in which at least one hydrogen is directly bonded to an aromatic ring, a) an aromatic iodine compound is used as a catalyst A first step of reacting in the absence of carbon monoxide and an aromatic carboxylic acid salt to obtain an aromatic carboxylic acid anhydride; and b) said aromatic carboxylic acid anhydride in the presence of an acylation catalyst. A method for producing an aromatic ketone, comprising a second step of reacting with an aromatic compound to obtain an aromatic ketone and an aromatic carboxylic acid.

In order to explain the method of the present invention in an easy-to-understand manner, an example of using an alkali metal salt of aromatic monoiodide or aromatic monocarboxylic acid is represented by the following reaction formula.

a) First step b) Second step Or / and Further, depending on the reaction conditions of the first step, when Ar ¹ ≠ Ar ² , some or all of the asymmetric aromatic carboxylic acid anhydride produced is disproportionate to two types of symmetrical aromatic carboxylic acid anhydrides. It may turn into.

Therefore, when a part of the asymmetric aromatic carboxylic acid anhydride is disproportionated, three kinds of aromatic carboxylic acid anhydrides coexist. In this case, in the second step, in addition to reaction formulas (2) and (3), in the reaction formula (2), Ar ² = Ar ¹
And the reaction (3 ′) when Ar ¹ = Ar ² in the reaction formula (3) occurs.

When all of the asymmetric aromatic carboxylic acid anhydrides are disproportionated into two types of symmetrical carboxylic acid anhydrides, in the second step, reaction formula (2 ′) and reaction formula (3 ′) Based reaction will occur.

(In the formula, A ¹ _r , A ² _r , and A ³ _r represent an aromatic group, and M represents an alkali metal atom.) In the first step of the present invention, the aromatic carboxylic acid anhydride is catalyst-free. It is characterized by high yield and high selectivity.
Further, since the by-product is a simple salt composed of the cation component of the aromatic carboxylate and the iodine anion, such as the alkali metal iodide exemplified in the above reaction formula (1), the aromatic carboxylic anhydride is used. Separation from an object is very easy, which is also one of the features of the present invention.

In the second step of the present invention, as exemplified by the above reaction formula (2) and / or (3), the aromatic carboxylic acid anhydride obtained in the first step in the presence of an acylation catalyst is used. The desired aromatic ketone can be obtained by reacting with an aromatic compound. In this case, since aromatic carboxylic acid is by-produced, it is recovered as a salt and
Recycling and reuse in the process is the preferred method.

Further, when A ¹ _r and A ² _r are the same aromatic residue, the process becomes simpler, and therefore, in one of the most preferred embodiments of the present invention.
It becomes one. For example, the reaction equation in this case is represented as follows.

(A ¹ _r , A ³ _r , and M are as described above) That is, since the aromatic carboxylic acid anhydride and the aromatic carboxylic acid salt are sequentially recycled, the aromatic iodine compound,
It shows that the target aromatic ketone can be obtained from carbon monoxide, an aromatic compound and an alkali metal hydroxide.

The aromatic iodine compound used in the present invention may be any compound as long as iodine is directly bonded to the aromatic ring. Examples of such aromatic iodine compounds include benzene, toluene, xylene, ethylbenzene, diethylbenzene, propylbenzene, quinene,
Compounds in which hydrogen in an aromatic ring of an aromatic hydrocarbon such as trimethylbenzene, tetramethylbenzene, naphthalene, anthracene is replaced by one or more iodine; compounds of an aromatic ring of a heteroaromatic compound such as pyridine, quinoline and bipyridine Compounds in which hydrogen is replaced by one or more iodine; Formula [However, A is a simple bond, or -O-, -S-,-
It represents a divalent group such as SO ₂ —, —CO—, —CH ₂ — and —C (R) ₂ — (R is a lower alkyl group). ] The compound etc. which hydrogen of the aromatic ring of the aromatic hydrocarbon shown by these was substituted by one or more iodine.
Further, in these aromatic iodine compounds, other substituents in which one or more hydrogens on the aromatic ring do not adversely affect the reaction, for example, a halogen atom other than iodine, a lower alkyl group, a lower alkoxy group, an ester group, a nitro group. It may be substituted with a substituent such as a group, an acyl group, an aroyl group, a carboxyl group, a cyano group or an amide group.

The aromatic carboxylate used in the present invention is a salt composed of an aromatic carboxylate anion as an anion component and various cation components. As the cation component, alkali metal, alkaline earth metal,
Monovalent or polyvalent metal cations such as copper, silver, zinc, mercury, silicon and tin; ammonium, substituted ammonium,
Onium cations such as substituted phosphonium are used. Among these aromatic carboxylates, alkali metal salts and alkaline earth metal salts are preferable, and alkali metal salts are particularly preferable.

Moreover, these aromatic carboxylates may contain two or more carboxylate groups in one molecule.

Examples of such an aromatic carboxylic acid salt include hydrogen of an aromatic ring of an aromatic hydrocarbon such as benzene, toluene, xylene, ethylbenzene, diethylbenzene, propylbenzene, quinene, trimethylbenzene, tetramethylbenzene, naphthalene, and anthracene. Compounds substituted with one or more carboxylate groups; pyridine,
Compounds in which hydrogen in the aromatic ring of a heteroaromatic compound such as quinoline or bipyridine is replaced by one or more carboxylate groups; [Wherein A is as described above] and the like in which the hydrogen of the aromatic ring is replaced by one or more carboxylate groups.

Further, in these aromatic carboxylic acid salts, other substituents in which one or more hydrogens on the aromatic ring do not adversely affect the reaction, for example, a halogen atom other than iodine, a lower alkyl group, a lower alkoxy group, an ester group, a nitro group. It may be substituted with a substituent such as a group, an acyl group, an aroyl group, a cyano group or an amide group.

A preferred embodiment of the first step of the present invention is a case where the aromatic residue of the aromatic iodine compound and the aromatic residue of the aromatic carboxylate are the same. In this case, a symmetrical aromatic carboxylic acid anhydride is obtained, and the process is simplified, as illustrated in the reaction formulas (4), (5), and (6) described above.

The carbon monoxide may be pure carbon monoxide, or may be diluted with another gas such as nitrogen, argon, helium, or lower hydrocarbon that does not adversely affect the reaction.
Carbon monoxide has a partial pressure of 0.1 to 300 kg / cm ² , preferably 1 to 20.
Used in the range of 0kg / cm ² .

In carrying out the first step, the molar ratio of the aromatic iodine compound and the aromatic carboxylate salt is not particularly limited, but preferably the iodine atom is relative to the cation component of the aromatic carboxylate salt. , 0.5 to 2.0 equivalents, more preferably
Used in the range of 0.8 to 1.5 equivalents.

Further, the first step can be carried out without using a reaction solvent, but it is a preferable method to use a solvent which does not adversely influence the reaction. Examples of such a solvent include aliphatic hydrocarbons such as hexane, heptane, octane, decane, and pentadecane; aliphatic hydrocarbons such as cyclohexane and methylcyclohexane;
Aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; Nitriles such as acetonitrile and benzonitrile; Sulfones such as sulfolane, methylsulfolane and dimethylsulfolane; Tetrahydrofuran, 1,
Ethers such as 4-dioxane and 1,2-dimethoxyethane; ketones such as acetone and methyl ethyl ketone; esters such as ethyl acetate and ethyl benzoate; N, N-dimethylformamide, N, N-dimethylacetamide, N-
Examples thereof include amides such as methylpyrrolidone and hexamethylphosphoramide.

The reaction of the first step is usually carried out at a temperature of 180 ° C. or higher,
It is preferably carried out at a temperature of 200 ° C. or higher and 400 ° C. or lower. Even more preferably, the temperature range is 230 ° C or higher and 350 ° C or lower. If the temperature is lower than 180 ° C., the reaction rate is slow and not practical, and if it is 400 ° C. or higher, side reactions increase and the yield of the target aromatic carboxylic acid anhydride decreases.

The reaction pressure in the first step is usually 1 to 500 kg / cm ² , preferably 5 to 300 kg / cm ² .

The reaction time is usually several minutes to several tens hours, though it varies depending on the kind and amount of the raw materials used or other reaction conditions such as temperature and pressure.

As the reaction system of the first step, any of a batch system, a continuous system and a combination thereof may be adopted.

According to such a method, in the first step, an aromatic carboxylic acid anhydride is obtained in a high yield and a high selectivity, and as a by-product, a salt composed of a cation component of the aromatic carboxylate and an iodine anion. Is obtained. Separation of aromatic acid anhydrides and such salts is easy. For example, when a solvent that dissolves an aromatic carboxylic acid anhydride but hardly dissolves an inorganic salt of iodine is used as a reaction solvent, it can be easily removed by filtration or decantation after the reaction. Can be separated into When such a solvent is not used as the reaction medium, it is also easy to extract the aromatic carboxylic acid anhydride from the reaction mixture after the reaction using such a solvent. Moreover, since many aromatic carboxylic acid anhydrides are stable in cold water, it is possible to extract salts from the reaction mixture with cold water.

In the second step of the present invention, the aromatic carboxylic acid anhydride thus obtained is reacted with an aromatic compound in the presence of an acylation catalyst to give the desired aromatic ketone and aromatic carboxylic acid. obtain.

The aromatic compound used in the second step may be any compound as long as at least one hydrogen atom is directly bonded to the aromatic ring. Examples of such aromatic compounds include benzene, toluene, xylene, ethylbenzene, diethylbenzene, propylbenzene, quinene,
Aromatic hydrocarbons such as trimethylbenzene, tetramethylbenzene, naphthalene, anthracene; pyridine,
Heteroaromatic compounds such as quinoline and bipyridine; Formula Aromatic hydrocarbons represented by [where A is as described above] and the like can be mentioned. Further, in these aromatic compounds, other substituents in which one or more hydrogens on the aromatic ring do not adversely affect the reaction, for example, a halogen atom, a lower alkyl group, a lower alkoxy group, an ester group, a nitro group, an acyl group, or an aroyl group. It may be substituted with a substituent such as a group, a carboxyl group, a cyano group or an amide group.

The acylation catalyst used in the second step is Friedel
Any substance can be used as long as it can carry out a Kraft-type acylation reaction, but it is preferable to use a Lewis acid and / or a strongly acidic protonic acid. Further, a solid catalyst containing a component exhibiting Lewis acidity is also preferable.

Such Lewis acids include boron, aluminum,
Halides of Group III elements such as gallium, indium, thallium, scandium, yttrium; silicon, germanium, tin, titanium, zirconium, etc.
Group IV element halides; antimony, bismuth,
Halides of Group V elements such as vanadium, niobium, and tantalum, and metal halides such as iron, copper, and zinc are used. Further, as strongly acidic protonic acids, hydrogen fluoride anhydride; fluorocarboxylic acids such as trifluoroacetic acid and perfluoropropionic acid; sulfonic acids such as methanesulfonic acid, ethanesulfonic acid and benzenesulfonic acid; fluorosulfonic acid, chlorosulfonic acid , Halogenated sulfonic acids such as trifluoromethanesulfonic acid, trichloromethanesulfonic acid, and perfluoroethanesulfonic acid, and halogenated alkanesulfonic acids. Further, a high-silica-containing zeolite which is a solid acid, a strongly acidic cation exchange resin, and acids called solid super strong acid can also be used. The solid super strong acid is a solid strong acid having an acid strength stronger than 100% sulfuric acid, and examples thereof include SbF ₅ , TaF ₅ , BF ₃ , CF ₃ SO ₃ H and Sb.
_{F 5 -HF, SbF 5 -FSO 3} H or a mixture thereof SiO ₂ -A
_{l 2 O 3, SiO 2 -TiO} 2, SiO 2 -ZrO 2, TiO 2 -ZrO 2, Al 2 O 3 -B
Supported on carriers such as ₂ O ₃ , SiO ₂ -WO ₃ , HF-zeolite, Al ₂ O ₃ , SiO ₂ , graphite, zirconium phosphate, cation exchange resin, activated carbon, various zeolites, and fluorinated graphite. Examples thereof include fluorinated sulfonic acid resins. Here, the fluorinated sulfonic acid resin is a resin having a —CF ₂ SO ₃ H group and / or a CFSO ₃ H group.

Further, the solid catalyst containing a component exhibiting Lewis acidity, such as supporting the Lewis acid as described above on a carrier as described above, a metal halide exhibiting Lewis acidity, for example CuC.
_{l 2, CuBr 2, AuCl 3} , AuBr 3, ZnCl 2, CdCl 2, HgCl 2, AlCl
₃ , AlBr ₃ , GaCl ₃ , GaBr ₃ , InCl ₃ , TlCl ₃ , TiF ₄ , ZrC
l ₄ , HfCl ₄ , NbF ₅ , NbCl ₅ , TaF ₅ , TaCl ₅ , SbF ₅ , SbF ₃ C
l ₂ , SbCl ₅ , CrCl ₃ , MoCl ₅ , WCl ₆ , MnCl ₂ , ReCl ₄ , FeC
l ₃ , CoCl ₃ , NiCl ₂ , RuCl ₃ , RhCl ₃ , PdCl ₂ , PdCl ₄ , IrCl
₄ , intercalation compounds with graphite such as PtCl ₄ . In these intercalation compounds, it is considered that the metal halide exists mainly as a monomolecular layer between the layers of the graphite and exchanges electrons with the graphite.

Furthermore, synthetic mica such as tetrasilicon mica and teniolite, natural mica such as muscovite, montmorillonite,
Kaolin, bentonite, aluminum ions exhibiting Lewis acidity of alkali metal ions and alkaline earth metal ions existing between layers of layered silicate compounds such as vermiculite, gallium ions, indium ions, titanium ions, zirconium ions, Antimony ion,
Those which are ion-exchanged with metal ions such as iron ions, nickel ions and copper ions are also preferably used as the solid catalyst showing Lewis acidity.

These acids can be used alone or in combination of two or more.

The use of a solid acid in the reaction system as an acylation catalyst is a preferable method because it is easy to separate and recover from the reaction product. In this case, the reaction may be carried out in a suspended state or as a fixed bed catalyst.

In carrying out the second step, the molar ratio of the aromatic carboxylic acid anhydride and the aromatic compound in which at least one hydrogen is directly bonded to the aromatic ring is not particularly limited, but is preferably The aromatic compound is used in an amount of 0.8 to 200 mol, more preferably 1 to 150 mol, per acid anhydride group of the aromatic carboxylic acid anhydride.

Further, the use ratio of the aromatic carboxylic acid anhydride and the acylation catalyst is not particularly limited, however, the acylation catalyst as an acid is usually 0.0001 to per aromatic carboxylic acid anhydride group.
It is carried out in the range of 1,000 equivalents, preferably 0.001 to 100 equivalents.

Further, in the second step, it is also preferable to use an aromatic compound as a reaction reagent in an excess amount as a reaction solvent, but it is also possible to use a solvent which does not adversely affect the reaction. Examples of such a solvent include carbon disulfide; halogenated hydrocarbons such as chloroform, methylene chloride, carbon tetrachloride, dichloroethane, trichloroethane and tetrachloroethane.

The temperature and time for carrying out the reaction of the second step will differ depending on other reaction conditions such as the type and amount of the acylation catalyst used, the type and amount of the reaction reagent, the presence or absence of a solvent, but are usually -30 to 35
The temperature is in the range of 0 ° C., preferably −10 to 300 ° C., and the range of several minutes to several tens hours. The reaction pressure may be usually atmospheric pressure, but if necessary, it may be carried out under pressure or under reduced pressure.

As the reaction system of the second step, any of a batch system, a continuous system and a combination thereof may be adopted.

According to such a method, in the second step, aromatic ketone is obtained in high yield and high selectivity, and aromatic carboxylic acid is obtained as a by-product. Aromatic carboxylic acids obtained as by-products include monovalent or polyvalent metal cations such as alkali metals, alkaline earth metals, copper, silver, zinc, mercury, silicon and tin, and ammonia, amines and phosphines. And the like to easily form an aromatic carboxylate salt. These carboxylic acid salts can be used as the aromatic carboxylic acid salts required in the first step, and therefore, they are preferably recycled and reused. This is one of the features of the present invention. For example, an alkali metal salt, which is one of the preferable aromatic carboxylic acid salts, can be easily prepared by a neutralization reaction between an aromatic carboxylic acid and an alkali metal oxide, hydroxide, carbonate or hydrogen carbonate. Can be obtained.

According to the method of the present invention, symmetrical and asymmetrical aromatic ketones can be obtained in high yield and high selectivity, but the aromatic iodine compound is iodobenzene or substituted iodobenzene, and the aromatic carboxylate is benzoic acid. A particularly preferable combination is an alkali metal salt of an acid or a substituted benzoic acid, and the aromatic compound is a substituted benzene. In this case, benzophenone or substituted benzophenone can be obtained in high yield and high selectivity. When the substituted iodobenzene is parahalogenoiodobenzene, the alkali metal salt of substituted benzoic acid is the alkali metal salt of parahalogenobenzoic acid, and the substituted benzene is morohalogenobenzene, 4,4′-dihalogenobenzophenone is obtained. It can be obtained efficiently (all halogens in this case refer to F, Cl and Br). Especially halogen is fluorine 4,
4'-Difluorobenzophenone is important as a monomer of an aromatic polyetherketone polymer having good heat resistance and chemical resistance, but it can be easily obtained by the method of the present invention.

〔The invention's effect〕

According to the method of the present invention, an aromatic ketone can be produced in good yield from an aromatic iodine compound, carbon monoxide and an aromatic compound in which at least one hydrogen is directly bonded to an aromatic ring.

〔Example〕

Hereinafter, the present invention will be further described with reference to examples, but the present invention is not limited to these examples.

Example 1 The first step was performed as follows.

50 mmol of parafluoroiodobenzene, 50 mmol of sodium parafluorobenzoate and 30 g of toluene were placed in a 200 ml autoclave (made by Hastelloy-C), and after substituting with carbon monoxide inside the autoclave, 100 kg / cm ² of carbon monoxide was injected under pressure. After reacting at 260-270 ° C for 2 hours with stirring,
After cooling, passing the reaction mixture and analyzing the liquid, the reaction rate of parafluoroiodobenzene was 100%, and the acid anhydride of parafluorobenzoic acid was obtained with a yield of 99% and a selectivity of 99%. I knew it. The acid anhydride of parafluorobenzoic acid was identified by gas chromatography, infrared absorption spectrum, and mass spectrum in agreement with the standard product. The slag was sodium iodide.

Acid anhydride of parafluorobenzoic acid obtained by distilling off toluene from the liquid, fluorobenzene 80 ml,
Teniolite catalyst ion-exchanged with aluminum ions
The second step was carried out by placing 2.8 g in an autoclave and reacting at 220-230 ° C. for 4 hours with stirring. After the reaction, the reaction mixture was cooled, the reaction mixture was passed, and the solution was analyzed. As a result, the reaction rate of the parafluorobenzoic acid anhydride was 100%
It was found that 4,4'-difluorobenzophenone was obtained with a yield of 96% and a selectivity of 96%. The slag consisted of a catalyst and about 50 mmol of parafluorobenzoic acid. By washing this slag with acetone, it was separated into an acetone solution of parafluorobenzoic acid and a solid acid teniolite catalyst. To parafluorobenzoic acid obtained by distilling off acetone from an acetone solution, an aqueous solution containing 50 mmol of sodium hydroxide was added to carry out a neutralization reaction, and then dehydration and drying were carried out to obtain sodium parafluorobenzoate. Was recovered.

Using the recovered sodium parafluorobenzoate, 50 mmol of parafluoroiodobenzene and 30 g of toluene under the same conditions, the reaction of the 1st step was carried out. As a result, an acid anhydride of parafluorobenzoic acid was obtained with almost the same results. Was given.

The teniolite catalyst ion-exchanged with aluminum ions used as the acylation catalyst in the second step was prepared by the following method.

Lithium teniolite 12 is a synthetic mica manufactured by Topy Industries, Ltd.
Add 600 ml of water to g and stir at room temperature for 1 hour, then about 15%
5 ml of hydrochloric acid was added to adjust the pH to 2-3. AlCl ₃・ 6H ₂ O 18.25g
Is dissolved in concentrated hydrochloric acid (10 ml) and water (10 ml).
An aqueous solution containing aluminum ions prepared by making up to 0 ml was added gently. With dilute NaOH solution
The pH was adjusted to 3 to 4, the mixture was stirred for 30 minutes, and then left overnight. Then, after filtration, washing with 0.2% dilute hydrochloric acid and pure water,
The teniolite catalyst ion-exchanged with aluminum ions was obtained by drying at 110-120 ℃ under reduced pressure overnight.

Example 2 Iodobenzene (50 mmol), potassium benzoate (50 mmol) and toluene (30 g) were used in the same manner as in Example 1 to perform the first step. As a result, benzoic anhydride was obtained in a yield of 99% and a selectivity of 99%. . Benzoic anhydride obtained by distilling off toluene from a toluene solution from which potassium iodide was removed, and an intercalation compound with graphite containing 35-40 W% AlCl ₃ .
The second step was carried out by placing 5 g of (Alfa Products Graphite AlCl ₃ -35) and 50 g of benzene in an autoclave and reacting at 150 to 160 ° C. for 5 hours with stirring. After the reaction, the mixture was cooled, the reaction mixture was passed, and the liquid was analyzed. As a result, it was found that benzophenone was obtained in a yield of 78% and a selectivity of 95%. Benzoic acid was produced as 82% by-product, which almost matched the reaction rate of benzoic anhydride. Benzoic acid could be recovered as potassium benzoate by reaction with potassium hydroxide, which could be reused in the first step.

Example 3 50 mmol of an acid anhydride of parafluorobenzoic acid obtained by the same method as in the first step of Example 1, fluorobenzene
100 mmol and 50 g of trifluoromethanesulfonic acid were placed in a flask, and the reaction was carried out at 75 to 78 ° C. for 5 hours with stirring. After completion of the reaction, excess fluorobenzene and trifluoromethanesulfonic acid were distilled off, cold water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with a dilute aqueous solution of sodium hydroxide and water in this order and dried. did. By distilling off the ethyl acetate, 4,4'-difluorobenzophenone was obtained with a yield of 94% and a selectivity of 96%.

Example 4 50 mmol of parachloroiodobenzene, 50 mmol of sodium parachlorobenzoate and 50 g of fluorobenzene were placed in an autoclave, and the inside was replaced with carbon monoxide.
After reacting at 0 ° C. for 3 hours, the mixture was cooled and passed to obtain a fluorobenzene solution of an acid anhydride of parachlorobenzoic acid. To this solution, 3.5 g of teniolite catalyst ion-exchanged with aluminum ions similar to that used in the second step of Example 1 was added, and reacted in an autoclave at 220 to 230 ° C. for 5 hours with stirring. The second step was performed. After the reaction, the reaction mixture was cooled, the reaction mixture was passed, and the liquid was analyzed. As a result, 4-chloro-4′-fluorobenzophenone was obtained in a yield of 92% and a selectivity of 93% based on parachloroiodobenzene. I knew I was there. Also, parachlorobenzoic acid was obtained from the slag by the same method as in Example 1.

Example 5 Paraiodoanisole (50 mmol), sodium paramethoxybenzoate (50 mmol) and toluene (30 g) were placed in an autoclave, the inside was replaced with carbon monoxide, and the mixture was reacted at 260 to 270 ° C. for 3 hours, then cooled and passed. Thus, a toluene solution of an acid anhydride of paramethoxybenzoic acid was obtained. By distilling off toluene, 30 ml of benzene and 100 mmol of anhydrous aluminum chloride were added to the obtained acid anhydride, and the mixture was reacted under reflux of benzene for 5 hours. After the reaction, excess benzene was distilled off, and dilute hydrochloric acid was added. Next, extraction is performed with ethyl acetate, and the extract is diluted with a sodium hydroxide aqueous solution,
It was washed with water in that order and dried. By distilling off ethyl acetate, paramethoxybenzophenone was obtained with a yield of 90% and a selectivity of 93%.

Example 6 Iodobenzene (50 mmol), sodium benzoate (50 mmol) and benzene (30 g) were used to carry out the first step in the same manner as in Example 1. As a result, benzoic anhydride was obtained in a yield of 99% and a selectivity of 99%. . Benzoic anhydride obtained by distilling off benzene from a benzene solution excluding sodium iodide, and 30 ml of fluorobenzene, and 2 g of a fluorinated sulfonic acid resin represented by the following formula were autoclaved. The mixture was placed in a flask and reacted at 150 ° C. for 5 hours with stirring. After the reaction
After separating the catalyst and benzoic acid, the fluorobenzene was distilled off, yielding 80% yield of 4-fluorobenzophenone.
%, The selectivity was 93%. The benzoic acid recovered by washing the slag with acetone was treated with a dilute aqueous sodium hydroxide solution, and then dehydrated and dried to easily obtain sodium benzoate. The first step was carried out using the sodium benzoate thus recovered, and benzoic anhydride was obtained with almost the same results.

Example 7 50 mmol of paramethyl iodobenzene, sodium benzoate
After putting 50 mmol and 50 g of toluene in the autoclave and replacing the inside of the autoclave with carbon monoxide, carbon monoxide
100 kg / cm ² was press-fitted. After reacting for 2 hours at 260-270 ° C under stirring, the mixture was cooled, the reaction mixture was filtered, and the filtrate was analyzed. The reaction rate of paramethyl iodobenzene was 100%.
Thus, it was found that paratoluic anhydride and benzoic anhydride were obtained with a yield of 99% and a selectivity of 99%, respectively. The filter cake was sodium iodide. The two carboxylic acid anhydrides as products were fixed by gas chromatography, infrared absorption spectrum, mass spectrum (GC-MS) and the like.

To a toluene solution containing two carboxylic acid anhydrides, 120 mmol of brine aluminum chloride was added and reacted at 100 ° C. for 4 hours. After the reaction, excess toluene was distilled off, diluted hydrochloric acid was added, and the mixture was extracted with ethyl acetate. The extract was washed with a dilute aqueous solution of sodium hydroxide and water in this order and dried. By distilling off the ethyl acetate, 4,4'- and 2,4'-dimethylbenzophenone were obtained in a yield of 92% and 4- and 2-methylbenzophenone in a yield of 93%.

The preferred embodiments of the present invention are as follows.

(1) A method according to claim 1, wherein the aromatic carboxylic acid by-produced in the second step is used as an aromatic carboxylic acid salt, and the carboxylic acid salt is circulated and reused in the first step (2) Aromatic iodine compound And the aromatic residue of the aromatic carboxylic acid salt is the same. (3) The aromatic carboxylic acid salt is an alkali metal salt of an aromatic carboxylic acid. Method described in the range (4) Method in which the acylation catalyst is Lewis acid and / or strongly acidic protic acid (5) Method in which the acylation catalyst is a solid catalyst containing a component showing Lewis acidity Patent (6) Aromatic iodine compound is iodobenzene or substituted iodobenzene, aromatic carboxylic acid salt is benzoic acid or an alkali metal salt of substituted benzoic acid, and aromatic compound is benzene or substituted benzene. And the resulting aromatic ketone is benzophenone or substituted benzophenone. (7) The substituted iodobenzene is parafluoroiodobenzene and the substituted benzoic acid alkali metal salt is an alkali of parafluorobenzoic acid. In the metal salt, the substituted benzene is fluorobenzene, and the resulting substituted benzophenone is 4,4′-
The method according to (7) above, which is difluorobenzophenone.

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Claims (1)

[Claims] 1. When an aromatic ketone is produced from an aromatic iodine compound, carbon monoxide and an aromatic compound in which at least one hydrogen atom is directly bonded to an aromatic ring, a) an aromatic iodine compound is used as a catalyst. A first step of reacting carbon monoxide and an aromatic carboxylic acid salt in the absence of an aromatic carboxylic acid salt at a temperature of 180 ° C. or higher to obtain an aromatic carboxylic acid anhydride; and b) acylating the aromatic carboxylic acid anhydride. A method for producing an aromatic ketone, which comprises a second step of reacting with the aromatic compound in the presence of a oxidization catalyst to obtain an aromatic ketone and an aromatic carboxylic acid.