JPH021704A - Polymer immobilized aminopyridinium salt derivative and production of aromatic fluorine compound using the same derivative as catalyst - Google Patents

Abstract

PURPOSE:To obtain the subject compound useful as a raw material for agricultural chemicals, etc., in a short time in high yield under a mild condition by reacting a specific halogenated aromatic compound with an alkali metal fluoride in the presence of a polymer immobilized aminopyridinium salt derivative catalyst. CONSTITUTION:A halogenated aromatic compound shown by formula II (n is 1-5 integer; Y is cyano, nitro, trifluoromethyl, etc.) is reacted with an alkali metal fluoride in the presence of a polymer immobilized aminopyridinium salt derivative catalyst shown by formula I (P is polymer supporting material by polystyrene skeleton; R<1> is alkylene; R<2> and R<3> are alkyl; X is halogen) to give an aromatic fluorine compound shown by formula III (Z is cyano, nitro, trifluoromethyl, formyl, etc.; m is 1-5 integer; n' is 0-4 integer; m+n'=n).

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a novel aminopyridinium salt derivative by immobilization on a polymer and an industrial method for producing an aromatic fluorine compound using the same as a catalyst.

(Prior art) In recent years, fluorine-containing agricultural chemicals and pharmaceuticals have attracted attention due to their excellent pharmacological and physiological activities, and have been actively researched. It is known to be an extremely important compound. Conventionally, various manufacturing methods have been devised as methods for manufacturing aromatic fluorine compounds. For example, aromatic compounds having a substituent such as a nitro group and further having a halogen substituent other than fluorine are treated with an alkali metal fluoride. A method for producing nuclear fluoroaromatic compounds has been known for a long time. (G. C. Finger et al., Journal of the American Chemical Society 4-
(J, Am, Chem, Soc,), 78, 60
(Page 34 (1956)) (Problems to be Solved by the Invention) However, the above method requires high reaction temperatures and a long time, does not provide a sufficient yield, and also produces by-products such as tar. In many cases, the results were unsatisfactory.

Furthermore, in order to solve these problems, methods of carrying out the fluorination reaction of halogenated aromatic compounds in the presence of various phase transfer catalysts have been studied.

For example, a method using a 4-aminopyridinium salt derivative (see published publication WO37104148) is known. In this method, 47.544% 4-fluoronitrobenzene was obtained by fluorination of 4-chloronitrobenzene with potassium fluoride, and although the yield was improved, the reaction temperature was as high as 210°C, and the catalyst used was This method was not fully satisfactory as an industrial method for producing aromatic fluorine compounds, as it was difficult to recover.

(Means for Solving the Problems) In view of the current situation, the present inventors believe that even when using as a raw material a compound that was conventionally thought to have poor reactivity among halogenated aromatic compounds, In order to provide a method for industrially producing aromatic fluorine compounds with high yield, we synthesized various catalysts and conducted extensive research.We found that the general formula ``Special Holiday'', R1 represents a linear or branched alkylene group, and Rz and R3 represents an alkyl group, and X represents a halogen atom. It was discovered that the novel polymer-immobilized aminopyridinium salt derivative shown in I was able to complete it.

That is, the present invention represents a general formula, R1 represents a straight chain or branched alkylene group, R2 and R3 represent an alkyl group, and X represents a halogen atom. ) In the presence of a polymer-immobilized aminopyridinium salt derivative represented by
In the formula, X represents a halogen atom, n represents an integer of 1 to 5, and when n is 2 or more, X may be a different halogen atom. Further, Y is a cyano group, a nitro group, a trifluoromethyl group, a formyl group, a group represented by the formula -COR'(R' represents a halogen atom, an alkyl group, or an aryl group), or a group represented by the formula -3OZR' (R ' represents a halogen atom, an alkyl group, or an aryl group). ) is reacted with an alkali metal fluoride to form a compound of the general formula (wherein, X has the same meaning as above, Z is a cyano group,
Nitro group, trifluoromethyl group, formyl L-COR
6 (R6 represents a fluorine atom, an alkyl group, or an aryl group) or a group represented by the formula -8O□R'(R' represents a fluorine atom, an alkyl group, or an aryl group in Table L) , m represents an integer from 1 to 5, n' represents an integer from O to 4, and m+n' = n. ) is a method for producing an aromatic fluoride compound, which is characterized in that a polymer-immobilized aminopyridinium salt derivative represented by the general formula (I) is used as a catalyst.

The polymer-immobilized aminopyridinium salt derivative of the present invention is a compound represented by the general formula (1), where R1 is, for example, methylene, ethylene, propylene,
1-20 carbon atoms such as tetramethylene, pentamethylene, hexamethylene, heptamethylene, l-methyldecylene, etc.
Preferably it represents a straight chain or branched alkylene group of 1 to 16, RZ.

R3 is a methyl group, an ethyl group, a propyl group, an i-propyl group, a butyl group, a pentyl group, or a hexyl group.

It represents an alkyl group having 1 to 10 carbon atoms such as an octyl group. In addition, ■ is a polymer support with a polystyrene skeleton, and the main skeleton is one or a mixture of styrene derivative monomers such as styrene, chlorostyrene, vinyltoluene, and α-methylstyrene, and in addition, divinylbenzene, ethylene dimethacrylate, etc. It is an insoluble polymer containing 1 to 20 mol% of a crosslinkable polymer.

The content of the aminopyridinium salt derivative immobilized on such a polystyrene polymer (ratio of aminopyridinium groups to all phenyl groups in the support polystyrene) is 5.
~60 mol%, preferably 10-40 mol%.

Furthermore, the polymer-immobilized aminopyridinium salt derivative represented by the general formula (1) of the present invention is manufactured by Macromolecular Hemi-Rabbit Communications (Macromolecular Hemi-Rabbit Communications).
kromol, Chem, Rapid Commmu
For example, as shown in the formula r, ω
- A 4-monoalkylaminopyridine derivative (
It can be synthesized by reacting V) to obtain polymer-immobilized aminopyridine l (VI), and further alkylating this.

(In the formula, ``RZR'', R' and X have the same meanings as above, and X'' represents a halogen atom.) Also, during this reaction, Alkylated polystyrenes are described, for example, in the Journal of
Macromolecular Science Chemistry (J,
Makromol, Sci-Chem, vol. 13, p. 767, (1979), Journal op.
Polymer Science Polymer Chemistry Edition (J, Polym, Sct, Polym, Ch
Em, Bd, Vol. 20, p. 3015, (1982) and Reactive Polymers (Reacttve.
Polyme Dings) Volume 3.

It can be synthesized according to the known method shown in literature such as p. 341 (1985). Further, specific examples of the 4-monoalkylaminopyridine derivative represented by the general formula (V) include 4-N-methylaminopyridine, 4-N-ethylaminopyridine, and 4-N-propylaminopyridine. , 4-N-butylaminopyridine and the like. In addition, the alkylation reaction includes 3-hebutyl bromide, 2-octyl bromide, 2-ethylhexyl bromide, 3-octyl bromide, 3-hebutyl methanesulfonate, 2-ethylhexyl methanesulfonate, 2-octyl It can be carried out according to a conventional method in the presence of an alkylating agent such as methanesulfonate, 3-octylmethanesulfonate, neopentyl bromide, neopentylmethanesulfonate, or the like.

Further, the polymer-immobilized aminopyridinium salt derivative represented by the general formula (1) can be obtained by reacting the halogenated aromatic compound represented by the general formula (I[) with an alkali metal fluoride to obtain the polymer-immobilized aminopyridinium salt derivative represented by the general formula (I[). It exhibits excellent activity as a catalyst for fluorination reactions in the method for producing aromatic fluorine compounds represented by [).

(In the formula, X, Y, Z, m, n and no have the same meanings as above, and MF represents an alkali metal fluoride.) In this production method, the halogenated aromatic compound used as a raw material is , is a compound represented by the general formula (n), where X represents a halogen atom such as a chlorine atom, a bromine atom, or an iodine atom, and n represents an integer from 1 to 5, and when n is 2 or more, X may be a different halogen atom, and Y is a cyano group, a nitro group, a trifluoromethyl group, or a formyl group of the formula -0OR'(R' represents a halogen atom, an alkyl group, or an aryl group). The group shown or the formula -So! A compound representing a group represented by R'(R' represents a halogen atom, an alkyl group, or an aryl group).

Specific examples of such halogenated aromatic compounds include benzonitriles such as 2-chlorobenzonitrile, 4-chlorobenzonitrile, and 2,6-dichlorobenzonitrile, 2-chloronitrobenzene, and 4-chloronitrobenzene. Nitrobenzenes such as 2-chlorobenzoic acid methyl ester, 4-chlorobenzoic acid ethyl ester, benzoic acid esters such as 3.4.5-) dichlorobenzoic acid methyl ester, 4-chlorobenzoyl chloride,
Benzoyl halides such as 2-chlorobenzoyl chloride, benzaldehydes such as 2-chlorobenzaldehyde and 4-chlorobenzaldehyde, aromatic ketones such as 4-chlorobenzophenone, 4゜4゛-dichlorobenzophenone, 4-chloroacetophenone, etc. Examples include benzenesulfonyl chlorides such as -chlorobenzenesulfonyl chloride and 4-chlorobenzenesulfonyl chloride, and aromatic sulfones such as 4-chlorophenylmethylsulfone and 4,4'-dichlorodiphenylsulfone.

Further, the aromatic fluorine compound obtained by the production method of the present invention is a compound represented by the general formula (III), where X has the same meaning as above, and Z represents a cyano group, a nitro group, Trifluoromethyl group.

Formyl group 1 formula -COR' (Rh is a fluorine atom.

Represents an alkyl group, an aryl group, and an aryl group. ) or a group represented by the formula -3O2R' (R? is a fluorine atom, an alkyl group,
Represents an aryl group. ), m is 1 to 5
represents an integer of 0 to 4, no represents an integer of 0 to 4, m+n'
= n, and Z in the case where Y in the general formula (II) contains a halogen atom other than a fluorine atom is one in which the halogen atom in Y is replaced with a fluorine atom. Specifically, such aromatic fluorine compounds include, for example, 2-
Benzonitriles such as fluorobenzonitrile and 2,6-cyfluorobenzonitrile, nitrobenzenes such as 2-fluoronitrobenzene and 4-fluoronitrobenzene, 2-fluorobenzoic acid methyl ester, 4-fluorobenzoic acid ethyl ester, 3゜4.5-) Benzoic acid esters such as refluorobenzoic acid methyl ester, 4-
Penzoyl fluorides such as fluorobenzoyl fluoride and 2-fluorobenzoyl fluoride, benzaldehydes such as 2-fluorobenzaldehyde and 4-fluorobenzaldehyde, 4-fluorobenzophenone,
4. Aromatic ketones such as 4'-difluorobenzophenone and 4-fluoroacetophenone, benzenesulfonyl fluorides such as 2-fluorobenzenesulfonyl fluoride and 4-fluorobenzenesulfonyl fluoride, 4-fluorophenylmethylsulfone, 4 , 4''-difluorodiphenylsulfone and other aromatic sulfones.

Examples of the alkali metal fluoride used in the method for producing an aromatic fluorine compound of the present invention include potassium fluoride and cesium fluoride, and spray-dried potassium fluoride is particularly preferred. These alkali metal fluorides are usually used in an amount of 1 to 2 equivalents to the halogen atom that can be substituted in the halogenated aromatic compound represented by the general formula (II). Furthermore, the polymer-immobilized aminopyridinium salt derivative represented by the above general formula (1) used as a catalyst has a pyridinium The amount of the group used is 1 to 50 mol%, preferably 5 to 20 mol%. Further, the reaction may be carried out without a solvent or in the presence of a solvent. Examples of the solvent used include halogenated hydrocarbon solvents such as chlorobenzene and chlorotoluene, and aprotic polar solvents such as acetonitrile, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, and sulfolane. The reaction temperature is usually room temperature to 300°C, preferably 50 to 250°C.
selected within the range. Furthermore, there is no particular restriction on the reaction pressure, and the reaction may be carried out at normal pressure or under an increased pressure of 1 kg/cm" or less, but from an industrial perspective, it is preferable to carry out the reaction at normal pressure. Further, a reaction time of about 1 to 20 hours is sufficient.

In addition, the polymer-immobilized aminopyridinium salt derivative used in this reaction can be easily recovered by filtration after being used as a catalyst, and after removing inorganic substances and tar by washing with water and solvent, it can be used in repeated reactions. I can do it.

(Effect of the invention) The polymer-immobilized aminovidinium salt derivative of the present invention is
It is a very useful compound as a catalyst for the fluorination of halogenated aromatic compounds, and the method for producing aromatic fluorine compounds using this as a catalyst involves the use of readily available halogenated aromatic compounds as raw materials. Aromatic fluorine compounds can be produced with high efficiency, and the fluorination reaction can proceed in a short time and with high yield even for compounds that were thought to have low reactivity, and furthermore, the catalyst used in the reaction can be recovered. It is an industrially excellent manufacturing method as it is easy and reusable.

(Example) Hereinafter, the present invention will be explained in more detail with reference to Examples.

Reference Example 1 [Synthesis of bromo-undecylated polystyrene] In a 4-tubular flask equipped with a stirrer and a cooler, 2 mol% divinylbenzene cross-linked polystyrene 15. Og (manufactured by Kodak), trifluoromethanesulfonic acid 2. 8g (19mn)
+ol), 1. 2-dichloropropane 70ml
was added, and the mixture was degassed by suction with an aspirator while stirring. After replacing the inside of the container with nitrogen gas and returning it to normal pressure, the temperature was increased to 45°C.
heated to. Then 10-bromoundecene14.
5 g (60 mmol) was dissolved in 1,2-dichloropropane, added dropwise at the same temperature, and further heated at 45 to 50°C for 41 hours.
The mixture was heated and stirred for hours. After the reaction was completed, the reaction mixture was cooled to room temperature and filtered, and the product was washed with dioxane, acetone, and tetrahydrofuran, and then dried with ventilation at 60° C. overnight. Bromoundecylated polystyrene was obtained by further drying under reduced pressure at 70°C for 5 hours.

The substitution rate due to weight increase was calculated to be 15.1%.

Reference Example 2 [Synthesis of polymer-immobilized aminopyridine] Sodium hydride (60%
% in mineral oil)1. The Og was taken out, 3Qml of n-hexane was added thereto, and after stirring for 2 to 3 minutes, it was allowed to stand, and the supernatant n-hexane was sucked up with a syringe to remove the mineral oil adhering to the sodium hydride. After repeating the same operation twice, the inside of the reaction vessel was reduced in pressure with an aspirator to remove all n-hexane,
The inside of the reaction system was replaced with nitrogen gas. 4-Methylaminopyridine 4. 6 g (42.5 mmol) was dissolved in anhydrous dimethylformamide 40n+1 and added dropwise at room temperature.

Thereafter, the mixture was stirred at room temperature for 1.5 hours, and 0.2 g of tetrabutylammonium bromide (0,62+++a+ol) and 20 g of bromo-undecylated polystyrene synthesized in Reference Example 1 were added, followed by stirring at room temperature for 16 hours under a nitrogen gas atmosphere. Thereafter, the mixture was heated to 60°C and stirred for 72 hours.

After the reaction was completed, the reaction mixture was cooled to room temperature and poured with 500ml of water.
1 and filtered, washed 3 times with 300ml of water,
Further, the product was washed with methanol, acetone, tetrahydrofuran, and dichloromethane, and then dried with ventilation at 50°C overnight.

Thereafter, it was dried under reduced pressure at 80 to 90°C for 4 hours, and 20.4g of polymer-immobilized aminopyridine (
i) was obtained.

300 mg of the obtained polymer was suspended in 30 ml of dioxane, and titrated with 0°1N methanol-hydrochloric acid using Congo red as an indicator.The content of aminopyridine was 1.
, 05 mmol/g.

Polymer-immobilized aminopyridine (i) Example 1 [Synthesis of polymer-immobilized aminopyridinium salt (1)] Polymer-immobilized aminopyridine (i) 1 obtained in Reference Example 2 was placed in a 200 m14 Turow flask equipped with a stirrer and a cooler.
8. 0 g (18.9 mmol), 2-ethylhexyl bromide 11. 6 g (60 mmol)
and 60ml of chlorobenzene, under nitrogen atmosphere,
The mixture was heated and stirred at 115 to 120°C for 17 hours.

After the reaction was completed, the reaction mixture was cooled and the solid polymer beads separated by filtration were washed with chlorobenzene, acetone, tetrahydrofuran and dichloromethane, washed again with acetone, and then dried with ventilation at 80° C. for one day. Furthermore, 3.5 at 80-90℃, 1-2 tmtaHg
By drying under reduced pressure for hours, 20.3 g of polymer-immobilized aminopyridinium salt (1) represented by formula (1) was obtained.

The bromide ion in this product was measured in the Journal of the
American Chemical Society (J, Am, C
hem, Soc, ), vol. 103, p. 3821 (19
It was analyzed according to the known method shown in 1981), and the content of aminopyridinium groups was determined from this value1.
It was 03 mn+ol/g. The results of infrared absorption spectrum analysis were as follows. ■R(Nujo
l); 1640 (C=C), 1600 (C=
N), 1550 (C=C).

820(C-H)cm-Polymer-immobilized aminopyridinium salt (1) Example 2 [Synthesis of polymer-immobilized aminopyridinium salt (2)] Reference example 2 from chlorohebutylated cross-linked polystyrene and N-methylaminopyridine Polymer-immobilized aminopyridine (2 mmol x divinylbenzene crosslinking, aminopyridine content 1.21 mmol/g) obtained in the same manner as 5.
0 g (6.05 mmol), 2-ethylhexyl bromide 11. Using 4 g (59 m+wol) and 30 ml of chlorobenzene, 5.7 g of polymer-immobilized aminopyridinium salt (2) represented by 2 (2) was obtained by the same operation as in Example 1.

The bromide ion in this product was analyzed in the same manner as in Example I, and the content of aminopyridinium groups determined from this was 1,
It was 02 mmol/g. The results of infrared absorption spectrum analysis were as follows.

I R (Nujol); 1640 (C=C), 1
600 (C=N), 1550 (C=C).

820 (C-11) cm-' zHs Example 3 Polymer-immobilized aminopyridine (2mmoJχ divinylbenzene crosslinked,
Contains aminopyridine if1.50+mol/g) 5.
0 g (7,50 mmol), 2-ethylhexyl bromide 14. Using 3 g (74 mmol) and 30 ml of chlorobenzene, 6.0 g of polymer-immobilized aminopyridinium salt (3) represented by formula (3) was obtained by the same operation as in Example 1.

The bromide ion in this product was analyzed in the same manner as in Example 1, and the content of aminopyridinium groups determined from this was 1. 0
It was 7+nmol/g. The results of infrared absorption spectrum analysis were as follows.

T R (Nujol); 1640 (C=C), 1
600 (C=N), 1540 (C=C).

820 (C-11) cm-' Polymer-immobilized aminopyridinium salt (3) Example 4 Spray-dried potassium fluoride (
manufactured by Riedel de Heen) 2.18g (37.5
mmol), take 1-2 mm (11 g), and at 150℃
Dry under reduced pressure for an hour. At the same time, in another round bottom flask, the polymer-immobilized aminopyridinium salt (1) synthesized in Example 1 as a catalyst 2. 45 g (25 mmol) was taken and dried under the same conditions, and after drying was completed, it was cooled and transferred into the 3-tube flask.

Furthermore, in the same container, 4-chloronitrobenzene 3, 9
After adding 4 g (25 mmol) and 15 g of anhydrous sulfolane and attaching a cooler and a stirrer, a heating stirring reaction was carried out at 180° C. for 4 hours in a nitrogen gas atmosphere.

After the reaction was completed, the reaction mixture was cooled and filtered.

After washing the obtained solid with 30 ml of dichloromethane, 30 ml of dichloromethane was further added and stirred at room temperature for 1 hour. Thereafter, it was filtered and the solid matter was washed with 30 ml of dichloromethane. After all the filtrates were combined and made homogeneous, analysis by gas chromatography revealed that 86% of 4-fluoronitrobenzene had been produced, and 3% of the raw material 4-chloronitrobenzene remained.

Furthermore, after concentrating this filtrate with a rotary evaporator,
Distillation under reduced pressure yielded 2.5 gt-13 of 4-fluoronitrobenzene with a boiling point of 77-82°C/6 mmHH.

The yield was 71%.

Further, the filtered catalyst and inorganic mixture was washed with water on a glass filter, and then washed with acetone. Furthermore, the recovered catalyst was added to 40 ml of tetrahydrofuran and 1 IN hydrochloric acid.
0ml was added and stirred at room temperature for 1 hour. Thereafter, it was filtered and washed with water repeatedly until the pH of the filtrate became about 7. Finally, after washing with tetrahydrofuran and drying with ventilation at 50°C for 1 day, the polymer-immobilized aminopyridinium salt (1) 2.3
3g was recovered.

Example 5 2.33 g of polymer-immobilized aminopyridinium salt (1) recovered in Example 4, 1 spray-dried potassium fluoride
．． 96 g (33.8 mmol), 4-chloronitrobenzene3. The reaction and post-treatment were carried out in the same manner as in Example 4, except that 55 g (22.5 mn+ol) and 12.5 g of anhydrous sulfolane were used. When the filtrates were mixed and analyzed by gas chromatography, no residual 4-chloronitrobenzene, a raw material, was found. Furthermore, 2.3 g of 4-fluoronitrobenzene was obtained by distillation. The yield was 72%.

Comparative Example 1 Polymer-immobilized aminopyridinium salt of Example 4 (1)
0.68 g (2,5 mmo
The same procedure as in Example 4 was carried out except that 1) was used. As a result of gas chromatography analysis, 68% of 4-fluoronitrobenzene was produced, and 32% of the raw material 4-chloronitrobenzene remained.

Comparative Example 2 Polymer-immobilized aminopyridinium salt (1) of Example 4
The same procedure as in Example 4 was carried out except that . As a result, 10% of 4-fluoronitrobenzene was produced, and 90% of the raw material 4-chloronitrobenzene remained.

After the reaction was completed, the mixture was cooled and filtered, and the solid matter was washed with 70 ml of dichloromethane. When the filtrates were mixed, 0.301 g of dibenzyl was added as an internal standard, and analyzed by gas chromatography, 44% of 4-fluorobenzonitrile was produced, and 3% of the raw material 4-chlorobenzonitrile was produced.
4% remained.

Example 6 1.54 g of polymer-immobilized aminopyridinium salt (3) and 1.31 g (22.5 mmol) of spray-dried potassium fluoride were placed in a 3-tube flask equipped with a stirrer and a water separator.
, 9 g of anhydrous sulfolane, and 20 ml of toluene were added, heated on an oil bath to distill off toluene, and azeotropic dehydration was performed. Continue heating until the liquid temperature reaches 140℃, then cool slightly,
Furthermore, the pressure inside the reaction vessel was reduced to 40 mm and 11 g to remove remaining toluene. After that, the temperature was lowered to 100°C or lower, and the atmosphere was replaced with nitrogen gas, and 4-chlorobenzonitrile 2.0
6 g (15 mmol) was added. Further, the mixture was heated and stirred at 215 to 220° C. for 6 hours under a nitrogen gas atmosphere. Anti-Comparative Example 3 The same procedure as in Example 6 was conducted except that the polymer-immobilized aminopyridinium salt (3) was not used in Example 6. As a result, the production rate of 4-fluorobenzonitrile was 11
%, and the residual rate of 4-chlorobenzonitrile is 81%.
Met.

Example 7 Potassium fluoride 3.4 spray dried in a 50 ml three-low flask equipped with water separator, thermometer and stirrer
9 g (60 mmol) 24 g anhydrous sulfolane 1 polymer-immobilized aminopyridinium salt (1) 3.85 g (4
, 0 mmol) was added.

Further, 20 ml of toluene was added and the mixture was heated and stirred, and the toluene was distilled off to perform azeotropic dehydration. The solution was heated until the temperature reached 150° C., then cooled, and the same amount of toluene was added, and the same dehydration treatment was repeated. After that, the pressure inside the flask was reduced to 30 nt/g using a vacuum pump, and the liquid temperature was further lowered to 150 nt/g.
C. to remove residual toluene. After cooling the inside of the reaction vessel to below 100°C and purging with nitrogen gas, 6.30 g (40 mmol) of 4-chloronitrobenzene was added.
The mixture was heated and stirred at 180° C. for 7 hours. When the same post-treatment as in Example 4 was performed and the dichloromethane solution was analyzed, it was found that 89% of 4-fluoronitrobenzene was produced and 2% of 4-chloronitrobenzene remained. Furthermore, 3.76 g of polymer-immobilized aminopyridinium salt (1) was recovered in the same manner as in Example 4. The recovery rate was 98%.

Example 8 To 3.76 g of polymer-immobilized aminopyridinium salt (1) recovered in Example 7, 90 μg of polymer-immobilized aminopyridinium salt (1) was added, and the rest were as in Example 7.
I did exactly the same operation. The production rate of 4-fluoronitrobenzene was 91%, and the residual rate of 4-chloronitrobenzene was 0.3%.

Example 9 By the same operation as in Example 8, using the polymer-immobilized aminopyridinium salt (1) recovered in the reaction of Example 8, a new polymer-immobilized aminopyridinium salt (1) corresponding to the reduced weight was added. The same reaction was repeated four times at 180° C. for 5 hours.

Each reaction solution was treated in the same manner as in Example 4, and the polymer-immobilized aminopyridinium salt (1) was repeatedly recovered. In the final reaction, 89% of 4-fluoronitrobenzene was produced, and 3% of 4-chloronitrobenzene was produced.
% remained. When this product was distilled under reduced pressure after distilling off the solvent, 4.63 g (yield: 82%) of 4-fluoronitrobenzene was obtained. The results of Examples 7 to 9 revealed that the polymer immobilized aminopyridinium salt (1) could be recovered and reused at least six times without deterioration in catalytic ability.

Example 10 Spray-dried potassium fluoride 3.49 in a third 50 ml flask equipped with a water separator, thermometer and stirrer.
g (60 mmol) 20 g anhydrous sulfolane, 1.90 g (2,
0 mmol) was added thereto, and azeotropic dehydration was performed with toluene in the same manner as in Example 6. 3.44 g (20 mmol) of 12.6-cyclobenzonitrile was added thereto, and the mixture was heated and stirred at 180° C. for 4 hours. Thereafter, the dichloromethane solution obtained was post-treated by the method shown in Example 4, and analyzed by gas chromatography. was being generated.

Dichloromethane was distilled off and 50 ml of ether and 30 ml of petroleum ether were added. Transfer this to a separating funnel,
The sulfolane was removed by washing three times with 100 ml of water. After drying the organic layer with anhydrous sodium sulfate, the solvent was distilled off to give 3.0
g of crude product was obtained. This is distilled in a kugelrohr,
2.28 g of 2.6-cyfluoropenzonitrile having a boiling point of 175° C./18 mm and 11 g was obtained. The yield was 82%.

Example 11 2.4-dichloro-3-fluoronitrobenzene was substituted for 2.6-dichlorobenzonitrile in Example 10.4.
Using 20 g (20 mmol), the mixture was heated and stirred at 180° C. for 2.5 hours. The boiling point was 180 to 90°C (Kugerrohr, external temperature) / 1 by the same post-treatment as in Example 10.
2.38 g of 2.3.4=trifluoronitrobenzene of 11 g of 5 mm was obtained. The yield was 67%. Further, by the same operation as in Example 4, 1.75 g of polymer-immobilized aminopyridinium salt (1) was recovered. Recovery rate 92%
Φ Example 12 To 1.75 g of polymer-immobilized aminopyridinium salt (1) recovered in Example 11, 0.15 g of polymer-immobilized aminopyridinium salt (1) was newly added, and Example 1
Potassium fluoride in the same amount as 1, anhydrous sulfolane, 2,4
- using dichloro 3-fluoronitrobenzene, 170
The reaction was carried out at ℃ for 2 hours. By the same isolation operation, 2.
3. 4 = 2.56 g of trifluoronitrobenzene
isolated. The yield was 72%.

Example 13 Azeotropic dehydration treatment was carried out in the same manner as in Example 10 using 1.74 g (30 mmol) of spray-dried potassium fluoride, 10 g of anhydrous sulfolane, 1.90 g (2 mmol) of polymer-immobilized aminopyridinium salt (1). went. 2 more
．． 3.50 g (20 mmol) of 3,4-dichlorobenzaldehyde was added instead of 6-dichlorobenzonitrile.

The mixture was heated and stirred at 200°C for 2 hours. When the reaction solution was analyzed by gas chromatography, it was found that 49% of 3-chloro-4-fluorobenzaldehyde was produced, and 3,
23% of 4-dichlorobenzaldehyde remained.

Example 14 In Example 10, 3,4-dichlorobenzoyl chloride 4. was used instead of 2,6-dichlorobenzonitrile.
Using 19 g (20 mmol), the reaction was carried out at 190° C. for 5 hours. When the reaction solution was analyzed by gas chromatography, it was found that no 3,4-dichloropenzoyl chloride, the raw material, remained, and 79% of 3-chloro-4-fluoropenzoyl fluoride was produced, and 3,4-difluoropenzoyl fluoride was produced. 9% fluoride was produced. Add 60 ml of dichloromethane to the obtained reaction solution, filter out inorganic substances,
After distillation, dichloromethane is concentrated and further distilled to a boiling point of 79
1.82 g of 3-chloro-4-fluoropenzoyl fluoride at ~80°C/10 mmtlg was obtained. Yield is 5
It was 2%.

Example 15 1.74 g (30 mmol) of spray-dried potassium fluoride, 10 g of anhydrous sulfolane, 1.47 g (1.5 mmol) of polymer-immobilized aminopyridinium salt (2)
The azeotropic dehydration treatment was carried out in the same manner as in Example 10. Next, 4-chlorobenzenesulfonyl chloride 3.1
7 g (15 mmol) was added and reacted at 200° C. for 7 hours.

When the reaction solution was analyzed by gas chromatography, it was found that 4
-65% of fluorobenzenesulfonyl fluoride and 25% of 4-chlorobenzenesulfonyl chloride were produced.

The reaction was carried out at 0°C for 7 hours. When the reaction solution was analyzed by gas chromatography, it was found that 2,4-difluoro-3,5-
52% neopentyl dichlorobenzoate was produced,
28% of its precursor, the nuclear monofluoro compound, remained.

Patent applicant: Ihara Chemical Industry Co., Ltd. Example 16

Claims (1)

[Claims] 1) General formula▲ Numerical formula, chemical formula, table, etc.▼ (In the formula, P represents a polymer support with a polystyrene skeleton, R^1 represents a linear or branched alkylene group, and R
^2 and R^3 represent an alkyl group, and X represents a halogen atom. ) Polymer-immobilized aminopyridinium salt derivative. 2) In the presence of a catalyst, there is a general formula ▲ mathematical formula, chemical formula, table, etc. ▼ (In the formula, X represents a halogen atom, n represents an integer from 1 to 5, and if n is 2 or more, X is different It may be a halogen atom.Also, Y is represented by a cyano group, a nitro group, a trifluoromethyl group, a formyl group, or the formula -COR^4 (R^4 represents a halogen atom, an alkyl group, or an aryl group). or a group represented by the formula -SO_2R^5 (R^5 represents a halogen atom, an alkyl group, or an aryl group). There are general formulas▲mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, X has the same meaning as above, Z is a cyano group,
Nitro group, trifluoromethyl group, formyl group, -CO
A group represented by R^6 (R^6 represents a fluorine atom, an alkyl group, or an aryl group) or a group represented by the formula -SO_2R^7 (
R^7 represents a fluorine atom, an alkyl group, or an aryl group. ), m represents an integer of 1 to 5, and n'
represents an integer from 0 to 4, and m+n'=n. ) In order to produce the aromatic fluorine compound represented by or a branched alkylene group, R^2 and R^3 represent an alkyl group, and X represents a halogen atom. Production method,