JPH0611719B2 - Method for producing diaryl iodonium fluoride - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to, for example, an insecticidal and acaricidal active compound and / or
Further, the present invention relates to a method for producing an intermediate for producing an aromatic fluorine compound which can be used as an intermediate for the synthesis of a drug or the like.

Currently, these aromatic fluorine compounds are produced by diazotizing an aromatic amine with sodium nitrate in anhydrous hydrogen fluoride and thermally decomposing it (West German Patent 600,
It is well known to those skilled in the art that No. 706) is industrially adopted. However, this method requires the use of a large excess amount of anhydrous hydrofluoric acid in order to suppress the production of phenolic impurities by the produced water.
The recovery of anhydrous hydrofluoric acid also has the drawback of being very difficult.

The present inventors have conducted extensive studies to overcome the above drawbacks and found that diaryl iodonium fluorides are good intermediates for easily producing an aromatic fluorinated compound (see Reference Examples below). .

[Conventional technology]

Conventionally, as a method for producing a diaryl iodonium fluoride, a corresponding diaryl iodonium halide is reacted with silver oxide and then reacted with hydrofluoric acid, or a diaryl iodonium halide is reacted with silver fluoride. Method [M. C. Caserio et al. A
m. Chem. Soc. , 81 , 336 (1959);
H. J. Emeleus et al. Chem. Soc. ，
1126 (1946). ] Are known, but these methods require excessive use of expensive silver compounds and are industrially difficult to use from an economical point of view.

[Problems to be solved by the invention]

As a result of intensive studies aimed at overcoming the above drawbacks, the present inventors have established a technique for producing diaryl iodonium fluorides easily and inexpensively, and completed the present invention.

[Means for solving problems]

The present invention has the general formula [Wherein, R ¹ and R ² represent a substituent independently selected from an alkyl group, a halogen atom, a nitro group, an alkoxy group, and an acylamino group, and m and n are 0 or an integer of 1 to 5] Represent ] By reacting a diaryl iodonium hydrogensulfate represented by the following with a hydrogen fluoride supplying substance in the presence of a basic barium compound, [R ¹ , R ² , m and n are the same as above. ] It manufactures the diaryliodonium fluoride represented by these.

As noted above, the R ¹ and R ² substituents in the present invention are each independently selected when m and n are each 2 or greater.

In the present invention, the alkyl group means an alkyl group having 1 to 8 carbon atoms which may be unsubstituted or substituted with a halogen atom or the like, and is methyl, ethyl, isopropyl,
Butyl, sec-butyl, t-butyl, pentyl, octyl, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, 1-chloroethyl, 1-bromoethyl, 1-iodoethyl and 2-bromoethyl. Including groups and the like. The halogen atom means a fluorine, chlorine, bromine or iodine atom. The alkoxy group means an alkoxy group having 1 to 8 carbon atoms which may be unsubstituted or substituted with a halogen atom or the like. The acylamino group is an acylamino group which may be unsubstituted or substituted with a halogen atom or the like, and includes an acetylamino group, a trifluoroacetylamino group, a benzoylamino group and the like. The diaryl iodonium hydrogensulfate represented by the general formula (I), which is the raw material of the present invention, is a compound that can be produced by various methods, and for example, (1) a method of reacting benzenes with iodosyl sulfate in sulfuric acid (2) Method of reacting benzene and potassium iodate in sulfuric acid-acetic anhydride [F. M. Beringer et al. Am. Ch
em. Soc. , 81, 342 (1959). ] (3)
It can be produced by a method of reacting iodobenzene with potassium persulfate in the presence of sulfuric acid (see the following reference example).

The present invention is to react a diaryl iodonium hydrogensulfate represented by the general formula (I) with a basic barium compound. Examples of the basic barium compound that can be used include barium hydroxide and barium oxide. The basic barium salt is used in an amount of 1 equivalent to a slight excess with respect to the diaryl iodonium hydrogensulfate represented by the general formula (I).

As the hydrogen fluoride-supplying substance which is another raw material of the present invention, various forms can be used, for example, anhydrous hydrofluoric acid, gaseous hydrogen fluoride, any solvent such as water and alcohol. Examples of the solution include a solution diluted with the above concentration, a hydrogen fluoride metal salt such as sodium hydrogen fluoride, potassium hydrogen fluoride, or the like. The hydrogen fluoride supply material is used in an amount of 1 equivalent to a slight excess with respect to the basic barium compound.

The order of addition is not particularly limited, but it is preferable to add the hydrogen fluoride supplying substance at the end in terms of yield.

In carrying out the present invention, it is preferable to use a solvent, and for example, polar solvents such as water, alcohol, acetonitrile, dimethylsulfoxide, dimethylformamide and the like can be used alone or in a mixture.

The reaction proceeds rapidly at room temperature, but the melting point of the solvent is 70 ° C.
It does not matter even if it is carried out in a temperature range of about a certain degree.

Hereinafter, the present invention will be described in more detail with reference to Examples.

Reference example 1 Concentrated sulfuric acid (1.3 ml, 24.4 mmol) was added dropwise at 0 ° C. to a mixed solution of iodobenzene (878 mg, 4.30 mmol), benzene (5 ml, 56 mmol) and acetic acid (5 ml). Then potassium persulfate (1.75 g, 6.45 mmol) was added,
The mixture was stirred at 0 ° C for 1 hour and at room temperature overnight. Ether under ice cooling 4
0 ml was added and the precipitated solid was collected by filtration. By recrystallizing the solid with ethanol-ether, 1.29 g (yield 80%) of diphenyliodonium hydrogensulfate was obtained.

Melting point: 165-166 ° C NMR (CD ₃ OD: TMS): δ 4.8 (bs, 1H), 7.53 (t, J = 8Hz, 4H), 7.
70 (t, J = 8Hz, 2H), 8.16 (d, J = 8Hz,
4H). Elemental analysis Calculated value as C ₁₂ H ₁₁ IO ₄ S C: 38.11, H: 2.93, S: 8.48% Measured value C: 37.93, H: 2.93, S: 8.49% Example 1 Diphenyliodonium hydrogen sulfate (302mg, 0.80mm
barium hydroxide (309 mg, 0.98 mmol) to a methanol solution (35 ml) of ol) and stirred well, then 1
N-HF methanol solution (1.5 ml, 1.5 mmol) was added. Diphenyliodonium fluoride was quantitatively obtained by removing the precipitated solid and concentrating under reduced pressure. ¹ H NMR (CD ₃ OD: TMS): δ 7.53 (t,
J = 8Hz, 4H), 7.69 (t, J = 8Hz, 2H),
8.17 (d, J = 8Hz, 4H). _{^{19 F NMR (CD 3 OD:}} CFCl 3): δ-160 (bs). Reference example 2 2 diphenyliodonium fluoride synthesized in Example 1
Heated at 00 ° C. for 5 minutes. As a result of GLC analysis of the reaction mixture, fluorobenzene (0.59 mmol, yield 74%) and iodobenzene (0.80 mmol, yield 100%) were formed. The structure of each product was determined by GLC fractionation and comparison of various spectral data with a standard product.

Example 2 Diphenyliodonium hydrogen sulfate (387mg, 1.02mm
barium hydroxide (420 mg, 1.33 mmol) was added to a methanol solution (10 ml) of ol) and stirred well, and then potassium hydrogen fluoride (157 mg, 2.01 mmol) was added. The solid was filtered off, the filtrate was concentrated, and a small amount of ethanol was added to remove the insoluble matter. The filtrate was concentrated under reduced pressure to obtain diphenyliodonium fluoride in a yield of 78%.

Reference example 3 To a mixed solution of p-iodotoluene (958 mg, 4.40 mmol), toluene (6 ml, 56.8 mmol) and acetic acid (5 ml) was added dropwise concentrated sulfuric acid 1.3 ml, 24.4 mmol at 0 ° C., followed by potassium persulfate (1.8 g). , 6.66 mmol),
The mixture was stirred at 0 ° C for 1 hour and at room temperature overnight. Ether under ice cooling 4
0 ml was added and the precipitated solid was collected by filtration. The solid was recrystallized from ethanol-ether to dihydrogensulfate (p-
Triyl) iodonium (1.38 g, yield 80%) was obtained.

Melting point: 168-169 ° C ¹ H NMR (CD ₃ OD: TMS): δ 2.40 (s,
6H), 4.8 (bs, 1H), 7.34 (d, J = 8Hz,
4H), 7.99 (d, J = 8Hz, 4H). Elemental analysis Calculated value as C ₁₄ H ₁₅ IO ₄ S C: 41.39, H: 3.72, S: 7.89% Measured value C: 41.23, H: 3.63, S: 8.09% Example 3 Di (p-tolyl) iodonium hydrogen sulfate (376mg, 0.85
barium hydroxide (309 mg, 0.98 mmol) was added to a methanol solution (40 ml) of (mmol) and stirred well.
A 1N-HF methanol solution (1.5 ml, 1.5 mmol) was added. The precipitated solid was removed and then concentrated under reduced pressure to quantitatively obtain di (p-tolyl) iodonium fluoride. ¹ H NMR (CD ₃ OD: TMS): δ 2.40 (s,
3H), 7.34 (d, J = 8Hz, 4H), 8.00 (d, J
= 8 Hz, 4H). ¹⁹ F NMR (CD ₃ OD: CFCl ₃ ): δ-167 (bs) Reference Example 4 The di (p-tolyl) iodonium fluoride synthesized in Example 3 was heated at 200 ° C. for 10 minutes. GLC of reaction mixture
As a result of the analysis, fluorobenzene (0.71 mmol, yield 7
1%) and iodobenzene (0.85 mmol, yield 10)
0%) was produced. The structure of each product was determined by GLC fractionation and comparison of various spectral data with a standard product.

Reference example 5 Concentrated sulfuric acid (1.3 ml, 24.4 mmol) and potassium persulfate (1.43 g, 5.28 mmol) were added to a mixed solution of iodobenzene (965 mg, 4.73 mmol), chlorobenzene (4.24 g, 47.0 mmol) and acetic acid (5 ml) at 0 ° C. In addition, 0 ℃
The mixture was stirred at room temperature for 1 hour and at room temperature for 3 days. Under ice cooling, ether 1
00 ml was added, and the precipitated solid was collected by filtration. The solid was recrystallized from ethanol-ether to give hydrogen sulfate (phenyl) (p-chlorophenyl) iodonium (1.26 g).
(Yield 65%) was obtained.

Melting point: 157-160.5 ° C ¹ H NMR (CD ₃ OD: TMS): δ 4.9 (bs, 1H), 7.55 (m, 4H), 7.71 (t, J.
= 8 Hz, 1H), 8.5 (m, 4H). Elemental analysis C ₁₂ H ₁₀ C1IO ₄ Calculated C as _{S · 1 / 4H 2 O:} 34.55, H: 2.48, S: 7.69% Found C: 34.53, H: 2.54, S: 7.83% Example 4 Hydrogen sulphate (phenyl) (p-chlorophenyl) iodonium (338mg, 0.82mmol) in methanol (4
Barium hydroxide (320 mg, 1.0 mmol) was added to 0 ml) and the mixture was stirred well, then 1N-HF methanol solution (1.5 ml,
1.5 mmol) was added. The precipitated solid was removed and then concentrated under reduced pressure to quantitatively obtain (phenyl) (p-chlorophenyl) iodonium fluoride. ¹ H NMR (CD ₃ OD: TMS): δ 7.55 (m, 4H), 7.71 (t, J = 8 Hz, 1H),
8.16 (m, 4H) ¹⁹ F NMR (CD ₃ OD: CFCl ₃ ): δ-165 (s) Reference Example 6 The (phenyl) (p-chlorophenyl) iodonium fluoride synthesized in Example 4 was heated at 200 ° C. for 10 minutes.
As a result of GLC analysis of the reaction mixture, fluorobenzene (0.
21 mmol, yield 26%), p-chlorofluorobenzene (0.26 mmol, yield 32%), iodobenzene (0.
33 mmol, yield 40%) and p-chloroiodobenzene (0.45 mmol, yield 55%) were produced. The structure of each product was determined by GLC fractionation and comparison of various spectral data with a standard product.

Reference example 7 p-chloroiodobenzene (1.15 g, 4.82 mmol),
A mixture of chlorobenzene (4.77g, 42.4mmol) and acetic acid (5ml) was added with concentrated sulfuric acid (1.3ml, 24.4mmo) at 0 ° C.
1) and potassium persulfate (1.45 g, 5.37 mmol) were added, and the mixture was stirred at 0 ° C. for 1 hour and at room temperature for 3 days. below freezing,
50 ml of ether was added and the precipitated solid was collected by filtration. The solid was recrystallized from ethanol-ether to obtain 1.33 g of di (p-chlorophenyl) iodonium hydrogensulfate (yield 62%).

Melting point: 168-169.5 ° C ¹ H NMR (CD ₃ OD: TMS): δ 4.8 (b
s, 1H), 7.57 (d, J = 8Hz, 4H), 8.15
(D, J = 8 Hz, 4H). Elemental analysis Calculated value as C ₁₂ H ₉ Cl ₂ IO ₄ S · 1 / 2H ₂ O C: 31.60, H: 2.10, S: 7.03% Actual value C: 31.56, H: 2.03, S: 7.31% Example 5 Di (p-chlorophenyl) iodonium hydrogen sulfate (37
Barium hydroxide (330 mg, 1.06 mmol) was added to a methanol solution (40 ml) of 5 mg, 0.84 mmol), and the mixture was well stirred and then 1N-HF methanol solution (1.5 ml, 1.5 mm).
ol) was added. The precipitated solid was removed and then concentrated under reduced pressure to quantitatively obtain di (p-chlorophenyl) iodonium fluoride. ¹ H NMR (CD ₃ OD: TMS): δ 7.56 (d, J = 8 Hz, 4 H), 8.16 (d, J = 8 H)
z, 4H). ¹⁹ F NMR (CD ₃ OD: CFCl ₃ ): δ-164 (s) Reference Example 8 The di (p-chlorophenyl) iodonium fluoride synthesized in Example 5 was heated at 200 ° C. for 10 minutes. As a result of GLC analysis of the reaction mixture, p-chlorofluorobenzene (0.
50 mmol, yield 60%) and p-chloroiodobenzene (0.84 mmol, yield 100%) were produced.
The structure of each product was determined by GLC fractionation and comparison of various spectral data with a standard product.

Reference example 9 p-Fluoroiodobenzene (0.80g, 3.6mmo
l), fluorobenzene (1.12 g, 11.6 mmol) and acetic acid (5 ml) at 0 ° C. in concentrated sulfuric acid (1.3 ml, 24.4
mmol) and potassium persulfate (1.08 g, 4.0 mmo
1) was added, and the mixture was stirred at 0 ° C. for 1 hour and at room temperature for 3 days. After cooling with ice, 100 ml of ether was added and the precipitated solid was collected by filtration.
The solid was recrystallized from methanol-ether to give di (p-fluorophenyl) iodonium hydrogen sulfate 1.25.
g (yield 83%) was obtained.

Melting point: 179-180 ° C ¹ H NMR (CD ₃ OD: TMS): δ 4.8 (bs,
1H), 7.30 (dd, J = 9, 8Hz, 4H), 8.23
(Dd, J = 9.5 Hz, 4H). Elemental analysis Calculated value as C ₁₂ H ₉ O ₄ SF ₂ C: 34.80, H: 2.19% Actual value C: 34.57, H: 2.17% Example 6 Di (p-fluorophenyl) iodonium hydrogen sulfate (3
Barium hydroxide (319 mg, 1.01 mmol) was added to a methanol solution (40 ml) of 24 mg, 0.78 mmol), and the mixture was well stirred and then 1N-HF methanol solution (1.5 ml, 1.5 m).
mol) was added. After removing the solid, the mixture was concentrated under reduced pressure to quantitatively obtain di (p-fluorophenyl) iodonium fluoride. ¹ H NMR (CD ₃ OD: TMS): δ 7.31 (dd, J = 9.1, 8.5 Hz, 4 H), 8.23 (d
t, J = 9.1, 4.8 Hz, 4H). ¹⁹ F NMR (CD ₃ OD: CFCl ₃ ): δ-105.5 (tt, J = 8.5, 4.8 Hz) -16
2.0 (bs) Reference Example 10 Fluorinated di (p-fluorophenyl) synthesized in Example 6
Iodonium was heated at 200 ° C. for 10 minutes. As a result of GLC analysis of the reaction mixture, p-difluorobenzene (0.34
mmol, yield 43%) and p-fluoroiodobenzene (0.67 mmol, yield 85%) were produced. The structure of each product was determined by GLC fractionation and comparison of various spectral data with a standard product.

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Claims (1)

[Claims] 1. A general formula [Wherein, R ¹ and R ² represent a substituent independently selected from an alkyl group, a halogen atom, a nitro group, an alkoxy group, and an acylamino group, and m and n are 0 or an integer of 1 to 5] Represents ] A general formula comprising reacting a diaryl iodonium hydrogensulfate represented by the following with a hydrogen fluoride supplying substance in the presence of a basic barium compound. [R ¹ , R ² , m and n are the same as above. ] The manufacturing method of the diaryl iodonium fluoride represented by these.