JPH0610165B2 - Process for producing fluorine-substituted aromatic carboxylic acid aryl ester - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a fluorine-substituted aromatic carboxylic acid which is an aromatic fluorine compound important as an intermediate for monomers for heat-resistant polymers or an intermediate for pesticides, pharmaceuticals and the like. It relates to a method for producing an aryl ester.

(Prior Art) A fluorine-substituted aromatic carboxylic acid aryl ester is a method of reacting a fluorine-substituted aromatic carboxylic acid and an aromatic hydroxy compound with a dehydrating condensing agent such as phosphorus oxychloride (Pharmaceutical Journal, Vol. 78, Vol. (P. 546, 1958)
Alternatively, it was produced by reacting a fluorine-substituted aromatic carboxylic acid chloride with an aromatic hydroxy compound. However, the fluorine-substituted aromatic carboxylic acid or fluorine-substituted aromatic carboxylic acid chloride as the raw material is expensive, and a dehydrating condensing agent such as phosphorus oxychloride is required in a stoichiometric amount, and its waste treatment is also required. It was troublesome and was a problem for industrial implementation.

On the other hand, it is also known that a non-fluorinated bromobenzene or iodobenzene derivative reacts with carbon monoxide and phenol in the presence of a palladium catalyst and a base to give a benzoic acid phenyl ester. (JP-A-59-29641).

However, little is known about the reaction between fluorine-substituted aromatic halide carbon monoxide and aromatic hydroxy compounds, which are compounds in which fluorine and halogen different from fluorine are directly bonded to the aromatic ring, and it is The effect of certain fluorine was not known at all.

(Means and Action of the Invention) As a result of continuing the study to develop a method capable of producing a fluorine-substituted aromatic carboxylic acid aryl ester from a fluorine-substituted aromatic halide in high yield, the present inventor found that palladium or a palladium compound was obtained. In the presence of a catalyst system consisting of a phosphine compound and a base, fluorine and a fluorine-substituted aromatic halide in which halogen different from fluorine is directly bonded to an aromatic ring together are reacted with carbon monoxide and an aromatic hydroxy compound. It was found that the target fluorine-substituted aromatic carboxylic acid aryl ester can be obtained in high yield and high selectivity, and a patent application was previously filed (Japanese Patent Application No. 60-26596).

As a result of further studies based on this finding, the present inventor has found that a nickel catalyst, which is a cheaper catalyst, can effectively advance this reaction, and completed the present invention.

That is, the present invention is directed to reacting a fluorine-substituted aromatic halide in which fluorine and a halogen different from fluorine are directly bonded to an aromatic ring together with carbon monoxide and an aromatic hydroxy compound in the presence of a nickel catalyst and a base. It is a method for producing a characteristic fluorine-substituted aromatic carboxylic acid aryl ester.

The nickel catalyst used in the present invention is not particularly limited as long as it contains a nickel element as a component, and nickel may be in a metallic state or may be a component forming a compound. The nickel component is, for example, activated carbon, graphite, silica, alumina, silica-alumina, silica-titania, titania, zirconia, barium sulfate, calcium carbonate, asbestos, bentonite,
Diatomaceous earth, polymer, ion exchange resin, zeolite,
It may be supported on a carrier such as molecular sieve, magnesium silicate, or magnesia.

On the other hand, compounds containing nickel include NiCl ₂ , NiBr ₂ and Ni.
Nickel halides such as I ₂ ; NiSO ₄ , Ni (NO ₃ ) ₂ , NiCO ₃ , Ni (SCN) ₂ , Ni (ClO ₄ ) ₂ and other inorganic acid nickel salts; Ni (OCOCH ₃ ) ₂ , Shu Nickel salts of organic acids such as nickel oxide; nickel oxide; nickel hydroxide; nickel sulfide; nickel phosphide; M ₂ [NiX ₄ ], M ₄
Nickelates represented by [NiX ₆ ] (M represents an alkali metal or ammonium ion, X represents a nitro group, a cyano group, halogen, NO ₃ , or 1 / 2SO ₄ ); [Ni (NH ₃ ) ₄ ] X ₂ , [Ni (Y) ₃ ] X ₂ , [Ni (Y) ₂ ] X ₂ , [Ni (p
y) ₄ ] Nickel ammine complexes such as X ₂ (X has the same meaning as described above, Y represents a chelating ligand such as ethylenediamine, diethylenetriamine, bipyridine, and phenanthroline, and py represents pyridine); Ni (aca
c) Chelate ligands such as ₂ are complex compounds (acac represents an acetylacetonate group); Ni (CO) ₄ , Ni (CO) ₃ (PR ₃ ), Ni (CO) ₂ (PR ₃ ) ₂ , NiX ₂ (PR ₃ ) ₂ , NiX (PR ₃ ) ₃ , Ni (PR ₃ ) ₄ , NiXPh (PR ₃ ) ₂ , Ni (RNC) ₂ , [NiX (allyl)] ₂ , N
i (C ₅ H ₅ ) ₂ , Ni (CO) ₂ (C ₅ H ₅ ) ₂ , NiX (C ₅ H ₅ ) (PR ₃ ), Ni (COD) ₂ , Ni (COD) (PR ₃ ), etc. Complex compounds or organic nickel compounds (R represents an organic group such as alkyl and aryl and COD represents cyclooctadiene) and the like are used. Note that some of these compounds may be used in the form of hydrates.

Further, other compounds may be added for the purpose of improving yield and selectivity. Examples of such compounds include phosphine compounds represented by the following general formula (I).

PR ′ ₁ R ′ ₂ R ′ ₃ (I) (In the formula, R ′ ₁ , R ′ ₂ , and R ′ ₃ are hydrogen, halogen, an aliphatic group, an alicyclic group, an aromatic group, and an araliphatic group. Represent
These may be the same or may be elements that constitute a ring containing phosphorus. Of course, it may be a polyphosphine compound containing two or more such phosphorus in one molecule.

Examples of such a phosphine compound include, for example, n-octylphosphine, di-n-butylphosphine, diethylbutylphosphine, tri-n-propylphosphine,
Alkylphosphines such as tri-n-butylphosphine, dialkylphosphines and trialkylphosphines; cycloaliphatic phosphines such as cyclohexylphosphine and dicyclohexylphosphine; fragrances such as benzylphosphine, dibenzylphosphine, dibenzylethylphosphine and tribenzylphosphine Aliphatic phosphines; mixed phosphines such as methylphenylphosphine, ethylphenylphosphine, dimethylphenylphosphine, methyldiphenylphosphine, methylbenzylphenylphosphine, ethyldiphenylphosphine, dicyclohexylphenylphosphine; phenylphosphine, Tolylphosphine, diphenylphosphine, triphenylphosphine, tristolylphosphine, diphenyltolylphosphine Which arylphosphine, diaryl phosphines and triarylphosphines, bis (diphenyl phosphino) methane, bis (diphenyl phosphino) ethane, ortho-phenylene-bis (diethyl phosphine, 2,2'-bis (diphenyl phosphine) -
Examples thereof include diphosphines such as 1-1'-binaphthyl.

The fluorine-substituted aromatic halide used as a raw material in the present invention may be any aromatic compound as long as fluorine and halogen different from fluorine are directly bonded to the aromatic ring as a substituent. Examples of such a fluorine-substituted aromatic halide include benzene and
Aromatic ring of aromatic hydrocarbons such as toluene, xylene, ethylbenzene, diethylbenzene, propylbenzene, cumene, trimethylbenzene, tetramethylbenzene, naphthalene, anthracene, etc., have one or more fluorine atoms and one or more other halogen atoms. Substituted compounds; Compounds in which hydrogen in the aromatic ring of a heteroaromatic compound such as pyridine, quinoline, bipyridine, etc. is substituted with one or more fluorine and one or more other halogen; [However, A is a simple bond, or -O-, -S-,-
_{SO 2 -, - CO -,} - CH 2 -, - C (R) 2 - (R
Represents a divalent group such as a lower alkyl group] and a hydrogen atom in the aromatic ring of the aromatic hydrocarbon represented by
Examples include compounds substituted with one or more other halogens.

Among these fluorine-substituted aromatic halides, a halogen species different from fluorine is bromine or iodine, which is excellent in the yield and selectivity of the desired reaction. Further, in these fluorine-substituted aromatic halides, other substituents that do not adversely influence the reaction, for example, lower alkyl group, lower alkoxy group, ester group,
It may be substituted with a substituent such as a nitro group or a cyano group.

Among such fluorine-substituted aromatic halides, a benzene derivative is particularly preferably used, and examples thereof include fluorochlorobenzene (each isomer), fluorobromobenzene (each isomer), fluoroiodobenzene (each isomer). Isomers) such as monofluoromonohalogenated benzenes; fluorodichlorobenzene (each isomer), fluorodibromobenzene (each isomer), fluorojodobenzene (each isomer), monofluorotribromobenzene (each isomer) ), Monofluorotriiodobenzene (each isomer), monofluorotetrabromobenzene (each isomer), and other monofluoropolyhalogenated benzenes; difluorochlorobenzene (each isomer), difluorobromobenzene (each isomer) , Difluoroiodobenzene (each isomer), trifluor Polyfluoromonohalogenated benzenes such as bromobenzene (each isomer) and pentafluorobrombenzene (each isomer); difluorodichlorobenzene (each isomer), difluorodibromobenzene (each isomer), difluorodiiodine Examples thereof include polyfluoropolyhalogenated benzenes such as benzene (each isomer), difluorotribromobenzene (each isomer), and trifluorodibromobenzene (each isomer).

Among these benzene derivatives, parafluorobromobenzene and parafluoroiodobenzene are particularly preferably used.

The aromatic hydroxyl compound used in the present invention may be any one as long as the hydroxyl group is directly bonded to the aromatic group. For example, phenol; cresol (each isomer), xylenol (each isomer), trimethylphenol (each isomer),
Various alkylphenols such as tetramethylphenol (each isomer), ethylphenol (each isomer), propylphenol (each isomer); methoxyphenol (each isomer), ethoxyphenol (each isomer) and various alkoxys Phenols; formula (However, A is as described above, and the aromatic ring may be substituted with a substituent such as a lower alkyl group, a lower alkoxy group, an ester group, a nitro group, and a cyano group.); (Each isomer) and various substituted naphthols; heteroaromatic hydroxyl compounds such as hydroxypyridine (each isomer), hydroxycoumarin (each isomer), hydroxyquinoline (each isomer); hydroquinone, resorcin, catechol, naphthohydroquinone Dihydroxy compounds such as anthrahydroquinone, and their alkyl-substituted dihydroxy compounds; Formulas (However, A is as described above, and the aromatic ring may be substituted with a substituent such as a lower alkyl group, a lower alkoxy group, an ester group, a nitro group and a cyano group.), Etc. Can be given.

Such aromatic hydroxy compounds may be used alone or in combination of two or more. Particularly preferred aromatic hydroxy compounds are phenol and 2,6
-2,6-dimethylphenol, which is xylenol.

The base used in the present invention may be either inorganic or organic. Examples of such a base include lithium oxide, lithium peroxide, sodium oxide, sodium peroxide, sodium superoxide, potassium oxide, potassium peroxide, dipotassium trioxide, potassium superoxide, rubidium oxide, rubidium peroxide, Rubidium trioxide, Rubidium superoxide, Rubidium ozonate,
Alkali metal oxides such as cesium oxide, cesium peroxide, cesium trioxide, cesium superoxide and cesium ozonide; beryllium oxide, magnesium oxide, calcium oxide, calcium superoxide, strontium oxide, strontium peroxide, barium oxide , Oxides of alkaline earth metals such as barium peroxide; lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide,
Alkali metal and alkaline earth metal hydroxides such as cesium hydroxide, beryllium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, and barium hydroxide; sodium carbonate, sodium hydrogen carbonate, potassium carbonate, hydrogen carbonate Salts of strong bases and weak acids such as potassium, barium carbonate, sodium silicate, magnesium silicate, potassium aluminate, calcium aluminate, sodium borate, barium borate; carbides such as calcium carbide and cesium carbide; aluminum hydroxide , Hydroxides and oxides of aluminum group metals such as potassium hydroxide, indium hydroxide, thallium hydroxide and thallium oxide; oxides and hydroxides of rare earth elements such as lanthanum oxide, cerium oxide and cerium hydroxide ; Lithium hydride, sodium hydride Hydride such as sodium borohydride, calcium hydride, lithium aluminum hydride; alkali metal or alkaline earth metal sulfide and sulfide such as sodium sulfide, sodium hydrogen sulfide, potassium sulfide, calcium sulfide; water Quaternary ammonium hydroxide compounds such as tetraethylammonium oxide and tetrapropylammonium hydroxide; Quaternary phosphonium hydroxide compounds such as methyltriphenylphosphonium hydroxide and tetramethylphosphonium hydroxide; trimethylsulfonium hydroxide and hydroxide Tertiary sulfonium hydroxide compounds such as triphenylsulfonium; salts of strong bases and weak organic acids such as sodium acetate, potassium benzoate, rubidium oxalate, barium propionate; sodium methylate, sodium ethyler Alkalates of alkali metal and alkaline earth metal such as calcium and ethylate; alkali metal and alkaline earth metal phenolates such as sodium phenolate, potassium phenolate, magnesium phenolate, and alkali metal of aromatic hydroxy compound used Salts or alkaline earth metal salts; amides of alkali metals and alkaline earth metals such as lithium amide, sodium amide, calcium amide, lithium dimethylamide; trimethylamine, triethylamine, tri-n-butylamine, triphenylamine, diethylmethylamine , N,
N-diethylaniline, N-methylpiperidine, N,
N'-diethylpiperazine, N-methylmorpholine, triethylenediamine, hexamethylenetetramine, N,
N, N ', N'-tetramethylethylenediamine, dicyclohexylethylamine, 1,2,2,6,6-pentamethylpiperidine, pyridine, quinoline, phenanthroline, indole, N-methylimidazole, 1,8
-Diazabicyclo- [5,4,0] -undecene-7
(DBU), 1,5-diazabicyclo- [4,3,0]
-Nonene-5 (DBN) and other tertiary amines and cyclic nitrogen-containing compounds (however, those having no NH group); crown ethers, azacrown ethers, thiacrown ethers, azacrowns and other crowns Compounds and complexes of these crown compounds with alkali metal or alkaline earth metal ions are used. further,
There may be two or more groups exhibiting these basicities in the molecule, or those forming a part of the polymer such as an anion exchange resin having a quaternary ammonium hydroxide group. Good. In addition, these basic substances or groups having basicity may be supported on a solid or chemically bound. These bases may be used alone or in combination of two or more.

The reaction of the present invention will be represented by the following reaction formula when the case of parafluorohalogenobenzene and phenol is illustrated.

(Z represents a halogen selected from Cl, Br and I.) As described above, one of the features of the method of the present invention is that only a halogen different from fluorine is substituted with an aryloxycarbonyl group, and fluorine is not substituted. Can be left in. It has been found that fluorine may not adversely affect this esterification reaction, or rather, it may have a favorable effect in terms of yield, selectivity and reaction rate.

In carrying out the present invention, nickel or a nickel compound is usually added to a fluorine-substituted aromatic halide in an amount of 0.
It is preferably used in an amount of 0001 to 1,000 times the molar amount. When a phosphine compound is used, if necessary, it is usually preferably used in an amount of 0.01 to 1,000 times the molar amount of nickel.

The aromatic hydroxy compound is preferably used in an amount of 1 to 1,000 times mol per halogen of the fluorine-substituted aromatic halide.

Further, it is preferable to use the base in an amount necessary for neutralizing the hydrogen halide to be formed, but it is needless to say that it may be less or more than this.

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 ³ , preferably 1 to
Used in the range of 200 kg / cm ³ .

In the method of the present invention, an aromatic hydroxy compound is preferably used in excess as a reaction solvent, but a solvent that does not adversely influence the reaction may be used if necessary. Examples of such a solvent include aliphatic hydrocarbons such as hexane, heptane, octane, decane, and pentadecane; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; benzene, toluene, xylene,
Aromatic hydrocarbons such as mesitylene; acetonitrile,
Nitriles such as benzonitrile; Sulfones such as sulfolane, methylsulfolane and dimethylsulfolane; Ethers such as tetrahydrofuran, 1,4-dioxane and 1,2-dimethoxyethane; Ketones such as acetone and methyl ethyl ketone; Ethyl acetate, benzoate Esters such as ethyl acid; N, N-dimethylformamide,
Examples thereof include amides such as N, N-dimethylaratoamide, N-methylpyrrolidone and hexamethylphosphoramide.

The reaction of the present invention is usually 50 to 350 ° C., preferably 10
In the range of 0 to 300 ° C., the reaction pressure is usually 1 to 5
It is carried out in the range of 00 kg / cm ³ , preferably 5 to 300 kg / cm ³ .

The reaction time varies depending on the type and amount of the catalyst system used and the starting materials, or other reaction conditions such as temperature and pressure, but it is usually several minutes to several tens hours.

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

(Effect of the Invention) It is clear that the method of the present invention can produce a fluorine-substituted aromatic carboxylic acid aryl ester from a fluorine-substituted aromatic halide, carbon monoxide and an aromatic hydroxy compound in high yield and high selectivity. became. This fluorine-substituted aromatic carboxylic acid aryl ester is not only used as an intermediate for agricultural chemicals, pharmaceuticals, etc., but also some of its compounds, for example, parafluorobenzoic acid phenyl ester and parafluorobenzoic acid 2,6-dimethylphenyl ester. Esters and the like are important as precursors of monomers for aromatic polyether ketones having excellent heat resistance and hot water resistance.
That is, these esters can be easily converted to 4- (parafluoronbenzoyl) phenol and 4- (parafluoronbenzoyl) -2,6-dimethylphenol, respectively, by rearrangement reaction, and these phenol derivatives themselves. , Or as one component of the copolymer,
This is because it can be used as a monomer of aromatic polyether ketone.

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

Example 1 Parafluoroiodobenzene 22.2 g, phenol 1
1.3 g, tri-n-butylamine 22.2 g, and nickel (II) acetylacetonate 0.77 g were put into the autoclave, the inside of the autoclave was replaced with carbon monoxide, and then carbon monoxide was injected into 50 kg / cm ³ . did. Under stirring, 2
After reacting at 00 to 220 ° C. for 2 hours, the mixture was cooled and the reaction solution was analyzed. As a result, the reaction rate of parafluoroiodobenzene was 100%, the yield of parafluorobenzoic acid phenyl ester was 95%, and the selectivity was 95. Obtained in%.

Example 2 Instead of phenol 2,6-dimethylphenol 14.
As a result of carrying out the reaction by the same method as in Example 1 except that 6 g was used, the reaction rate of parafluoroiodobenzene was 98%, and the yield of parafluorobenzoic acid 2,6-dimethylphenyl ester was 93%. Obtained with a selectivity of 95%.

Example 3 17.5 g of parafluorobromobenzene, phenol 1
1.3 g, tri-n-butylamine 22.2 g, NiC
0.65 g of 1 _{2 and} 2.6 g of triphenylphosphine were placed in an autoclave, the inside of the autoclave was replaced with carbon monoxide, and then carbon monoxide was injected under pressure of 50 kg / cm ³ .
After reacting at 210 to 230 ° C. for 2 hours under stirring, the mixture was cooled, and the reaction solution was analyzed. As a result, the reaction rate of parafluorobromobenzene was 95%, and the yield of parafluorobenzoic acid phenyl ester was 81%. The selectivity was obtained at 85%.

Example 4 A reaction was carried out in the same manner as in Example 1 except that 17 g of β-naphthol was used instead of phenol, and as a result, parafluorobenzoic acid β-naphthyl ester was obtained with a yield of 90% and a selectivity of 92%. Was given.

Example 5 The reaction was carried out in the same manner as in Example 1 except that nickel (II) acetylacetonate was replaced by 0.7 g of nickel (II) tetrahydrate, resulting in the reaction of parafluoroiodobenzene. The yield was 97%, and parafluorobenzoic acid phenyl ester was obtained with a yield of 92% and a selectivity of 95%.

Example 6 Parafluoroiodobenzene 22.2 g, phenol 1
1.3 g, tri-n-butylamine 22.2 g, NiC
The reaction was carried out in the same manner as in Example 1 using 0.5 g of l ₂ [P (C ₆ H ₅ ) ₃ ] ₂ and as a result, parafluorobenzoic acid phenyl ester was obtained in a yield of 92% and a selectivity of 95. Obtained in%.

Example 7 Using 14.4 g of 2-fluoro-4-chlorotoluene, 23 g of phenol, 13 g of sodium phenoxide, 0.9 g of nickel acetate, and 2.5 g of triphenylphosphine, carbon monoxide was pressed into 150 kg / cm ^3. , Under stirring 260
As a result of reacting at 5 ° C. for 5 hours, the reaction rate of 2-fluoro-4-chlorotoluene was 58%, the yield of phenyl ester of 3-fluoro-4-methylbenzoic acid was 40%, and the selectivity was 70.
Obtained in%.

Example 8 2-Fluoro-6 in place of parafluoroiodobenzene
-A reaction was carried out in the same manner as in Example 1 except that 22.5 g of iodonaphthalene was used, and as a result, 2-fluoronaphthalene-6-carboxylic acid phenyl ester was obtained with a yield of 92% and a selectivity of 95%. It was

Example 9 11.1 g of parafluoroiodobenzene, phenol 4
5 g, sodium phenoxide 6.96 g, nickel (I
I) Using 0.7 g of acetylacetonate, the reaction was carried out in the same manner as in Example 1. As a result, the reaction rate of parafluoroiodobenzene was 95%, and the yield of parafluorobenzoic acid phenyl ester was 94%. Obtained with a selectivity of 99%.

Example 10 Parafluoroiodobenzene 22.2 g, phenol 1
1.3 g, tri-n-butylamine 22.2 g, NiC
0.1 g of 1 _{2 and} 0.2 g of triphenylphosphine were placed in an autoclave and the reaction was carried out in the same manner as in Example 1. As a result, the reaction rate of parafluoroiodobenzene was 100%, and parafluorobenzoic acid phenyl ester was obtained. Was obtained with a yield of 97% and a selectivity of 97%.

As a result of performing a completely similar reaction without using triphenylphosphine, the reaction rate of parafluoroiodobenzene was 35.
%, The yield of parafluorobenzoic acid phenyl ester was 34%, but the selectivity was as high as 97%.

Example 11 The reaction was carried out in the same manner as in Example 1 except that 9.4 g of pyridine was used instead of tri-n-butylamine, and as a result, the yield of parafluorobenzoic acid phenyl ester was 96.
%, Selectivity 97%.

Example 12 20.4 g of paraphenylphenol instead of phenol
As a result of carrying out the reaction in the same manner as in Example 1 except that was used, parafluorobenzoic acid paraphenylphenyl ester was obtained with a yield of 95% and a selectivity of 96%.

Examples 13 to 16 Parafluoroiodobenzene 22.2 g (0.1 mol), phenol 11.3 g (0.12 mol), tri-
Using 22.2 g (0.12 mol) of n-butylamine,
In the presence of various catalyst systems, carbon monoxide 50 kg / cm ³ , 20
The following table shows the results obtained by carrying out the reaction for 2 hours under stirring at 0 to 210 ° C.

In the table, Ph represents a phenyl group.

Continuation of front page (51) Int.Cl. ⁵ Identification code Office reference number FI Technical display location B01J 27/24 X 9342-4G 31/28 X 7821-4G C07C 67/36 69/78 9279-4H // C07B 61/00 300

Claims (6)

[Claims] 1. A fluorine-substituted aromatic halide in which fluorine and a halogen different from fluorine are directly bonded to an aromatic ring together with a carbon monoxide and an aromatic hydroxy compound in the presence of a nickel catalyst and a base. And a method of producing a fluorine-substituted aromatic carboxylic acid aryl ester. 2. The method according to claim 1, wherein the halogen different from fluorine is bromine or iodine. 3. The fluorine-substituted aromatic halide in which both fluorine and halogen different from fluorine are directly bonded to an aromatic ring are benzene derivatives having fluorine and halogen different from fluorine as a substituent. The method according to item 2. 4. The method according to claim 3, wherein the benzene derivative is parafluorobromobenzene or parafluoroiodobenzene. 5. The method according to any one of claims 1 to 4, wherein the aromatic hydroxy compound is an aromatic monohydroxy compound. 6. The method according to any one of claims 1 to 4, wherein the aromatic hydroxy compound is phenol and / or 2,6-dimethylphenol.