JPH0656821A - @(3754/24)haloalkyl)dibenzotellurophenium salt, intermediate for producing the same and their production - Google Patents

Abstract

PURPOSE:To obtain a new (haloalkyl)dibenzotellurophenium salt useful as a new reagent for organic synthesis and as an organic new material. CONSTITUTION:A compound of formula I (R<1> and R<2> are each H or an electron absorbing group; Rf is a 1-10C haloalkyl; X<-> is a conjugated base of Bronsted acid), e.g. Te-(n-heptafluoropropyl)dibenzotellurophenium trifluoromethane sulfonate. This compound is obtained from a new (haloalkyl)tellurobiphenyl of formula III obtained by reacting bis(2-biphenyl)ditelluride of formula II with a reducing agent and a halogenated haloalkyl of the formula Rf-Y (Y is a halogen). For example, a compound of formula III is made to react with a halogen and a Bronsted acid or a Lewis acid to provide the compound of formula IV or the compound of formula III is made to react with a sulfoxide of formula V and a sulfonic acid derivative of the formula VI to provide the (haloalkyl) dibenzotellurophenium sulfonate of formula VII.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel (haloalkyl) dibenzotellophenium salt useful as a reagent for organic synthesis or as a new organic material, a production intermediate thereof, and a production method thereof.

[0002]

2. Description of the Related Art Organic tellurium compounds have recently attracted attention as reagents in synthetic organic chemistry or as new organic materials.

Regarding organic tellurium compounds as conventionally known reagents, for example, N. Petragnani, JV Comasseto, S.
synthesis, 1991 , 793-817, and 1991 , 897-919. Regarding the properties as an organic material, see N.
S. Dance, CHW Johes, Can. J. Chem., 56 , 1746-1
751 (1978).

[0004]

DISCLOSURE OF THE INVENTION The present invention provides a (haloalkyl) dibenzotellophenium salt, which is a novel organic tellurium compound useful as a new reagent for organic synthesis and as a new organic material, an intermediate for producing the same, and It is intended to provide a method for producing them.

[0005]

That is, the present invention provides a compound represented by the general formula (I):

[Chemical 18] A (haloalkyl) dibenzotellophenium salt represented by and a production intermediate thereof, represented by the general formula (II):

[Chemical 19] (In this general formula, Rf is a haloalkyl group having 1 to 10 carbon atoms.) The present invention relates to (haloalkyl) tellurobiphenyl.

According to the present invention, further, bis (2-biphenyl) ditelluride, a reducing agent and a haloalkyl halide are reacted to obtain the above-mentioned intermediate (II) of the formula (haloalkyl) tellurobiphenyl. Then, a method for producing the above-mentioned (haloalkyl) dibenzotellophenium salt is provided by reacting this with halogen and a Bronsted acid or a Lewis acid, and if necessary, then performing nitration and the like. It

Alternatively, the above-mentioned (haloalkyl) is prepared by reacting the above-mentioned 2- (haloalkylteluro) biphenyl with a sulfoxide and a sulfonic acid derivative.
A method of making dibenzotellophenium sulfonate is provided.

Further, there is provided a method for producing another (haloalkyl) dibenzotellophenium salt by reacting the above (haloalkyl) dibenzotellophenium salt with a Bronsted acid salt.

The present invention will be described in detail below. The (haloalkyl) dibenzotellophenium salt of the general formula (I) according to the present invention has a novel organic tellurium structure in which a haloalkyl group which is an electron-withdrawing group is bonded to the tellurium atom of the dibenzotellophenium skeleton. According to this structure, by converting R ¹ and R ² from a hydrogen atom into an electron-withdrawing group such as a nitro group, the electron density of the tellurium atom can be further reduced, and therefore, as a new reagent for organic synthesis, , It will be useful as a new organic material.

In the compounds of the present invention including the above general formula (I), Rf is, for example, trifluoromethyl,
Perfluoroethyl, perfluoro-n-propyl, perfluoroisopropyl, perfluoro-n-butyl,
Perfluoroisobutyl, perfluoro-t-butyl,
Perfluoropentyl, perfluorohexyl, perfluoroheptyl, perfluorooctyl, perfluorononyl, perfluorodecyl, difluoromethyl, fluoromethyl, tetrafluoroethyl, trifluoroethyl, hexafluoropropyl, octafluorobutyl,
Decafluoropentyl, dodecafluorohexyl, tetradecafluoroheptyl, hexadecafluorooctyl, octadecafluorononyl, icosafluorodecyl, trichloromethyl, trifluorodichloroethyl,
It may be a straight-chain or branched haloalkyl group having 1 to 10 carbon atoms such as bromotetrafluoroethyl, iodotetrafluoroethyl, iodoperfluorobutyl and iodoperfluorooctyl.

[0011]

[Chemical 20] For example, a hydrogen halide conjugate base consisting of HF, HCl, HBr, and HI; methanesulfonic acid, ethanesulfonic acid, butanesulfonic acid, benzenesulfonic acid, nitrobenzenesulfonic acid, dinitrobenzenesulfonic acid, toluenesulfonic acid, trichloromethanesulfone. Acid, trifluoromethanesulfonic acid, difluoromethanesulfonic acid, trifluoroethanesulfonic acid, tetrafluoroethanesulfonic acid, perfluorobutanesulfonic acid, perfluorooctanesulfonic acid, 10-camphorsulfonic acid, 3-bromocamphor-8-sulfonic acid, Conjugate bases of sulfonic acids such as sulfuric acid, chlorosulfonic acid, fluorosulfonic acid; formic acid, acetic acid, propionic acid, chloroacetic acid, dichloroacetic acid,
Conjugate bases of carboxylic acids such as trichloroacetic acid, trifluoroacetic acid, benzoic acid, chlorobenzoic acid, nitrobenzoic acid and dinitrobenzoic acid; HBF ₄ , HBCl ₄ , HBF ₃ Cl, HSbF ₆ , HS
bCl ₅ F, HSbCl ₆ , HAsF ₄ , HAsF ₆ , HAlCl ₄ , HAlCl ₃ F,
A conjugate base of an acid consisting of a Lewis acid such as HPF ₄ and HPF ₆ and hydrogen halide; HBPh ₄ ,

[Chemical 21] Examples thereof include conjugate bases of acids such as boron; conjugate bases of nitric acid; conjugate bases of halogen acids such as perchloric acid, perbromic acid, periodic acid and hypochlorous acid.

Further, in the present invention, in the (haloalkyl) tellurobiphenyl of the general formula (II) which is a novel intermediate for production, Rf is the same as Rf contained in the general formula (I), The same thing as what was done can be illustrated.

The (haloalkyl) dibenzotellophenium salt represented by the general formula (I) can be produced according to the following reaction formula i.

Reaction formula i

[Chemical 22]

[I-1 step] In this step, the above-mentioned screw (2
-Biphenyl) ditelluride, a reducing agent and a haloalkyl halide represented by the above formula (VII) are reacted to produce a (haloalkyl) tellurobiphenyl represented by the above formula (II).

As a procedure of this production process, bis (2-biphenyl) ditelluride is reacted with a reducing agent, followed by
The compound of formula (VII) may be reacted, or the reducing agent may be reacted with bis (2-biphenyl) ditelluride in the presence of the compound of formula (VII).

Bis (2-biphenyl) ditelluride used in this step is a known compound and can be easily produced by a known method [Can. J. Chem., 56 , 1746-.
1751 (1978) and Synthesis, 1986 , 1-30].

Further, the haloalkyl halide of the formula (VII) is an industrially available compound, for example, trifluoromethyl bromide, trifluoromethyl iodide, perfluoroethyl bromide, perfluoroethyl iodide, Perfluoropropyl bromide, perfluoropropyl iodide, perfluorobutyl bromide, perfluorobutyl iodide, perfluoropentyl bromide, perfluoropentyl iodide, perfluorohexyl bromide, perfluorohexyl iodide, perfluorooctyl bromide, perfluorooctyl iodide, Perfluorononyl bromide, perfluorononyl iodide, perfluorodecyl bromide, perfluorodecyl iodide, difluoromethyl bromide, difluoromethyl iodide, fluoromethyl bromide, fluoromethyl iodide, trichloromethyl bromide Le iodide trichloromethyl,
Trifluorodichloroethyl bromide, trifluorodichloroethyl iodide, tetrafluoroethyl bromide, tetrafluoroethyl iodide, trifluoroethyl bromide, trifluoroethyl iodide, hexafluoropropyl bromide, hexafluoropropyl iodide, Octafluorobutyl bromide, octafluorobutyl iodide, dodecafluorohexyl bromide, dodecafluorohexyl iodide, hexadecafluorooctyl bromide, hexadecafluorooctyl iodide, icosafluorodecyl bromide, icosafluoroiodide Examples thereof include linear or branched haloalkyl bromide or haloalkyl iodide such as decyl, dibromotetrafluoroethane, diiodotetrafluoroethane, diiodoperfluorobutane, and diiodoperfluorooctane.

On the other hand, the reducing agent can be selected from the reducing agents usually used in organic reactions. For example, alkali metals such as sodium, potassium and lithium, sodium borohydride, lithium borohydride,
_{NaBH 3 (OCH 3), NaBH} 2 (OCH 3) 2, NaBH (OCH 3) 3, NaBH 3 (OE
_{t), NaBH 3 [OCH (} CH 3) 2], aluminum hydride, lithium aluminum _{hydride, LiAlH 3 (OCH 3),} LiAlH 2 (OCH 3) 2,
Examples thereof include aluminum hydride compounds such as LiAlH (OCH ₃ ) ₃ , LiAlH ₃ (OEt), and LiAlH ₃ [OC (CH ₃ ) ₃ ].

In this step, it is usually preferable to carry out the reaction in a solvent, and examples of the solvent that can be used include dimethylformamide (DMF), dimethylacetamide, dimethyl sulfoxide, dimethyl sulfone, tetramethylene sulfone, dimethyl ether, tetrahydrofuran. ,
Solvents such as liquid ammonia, methylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, acetone, acetonitrile, methanol, ethanol, propyl alcohol, butyl alcohol, diglyme and the like, or a mixed solvent thereof is preferable.

The reaction temperature can be generally selected from the range of about -80 ° C to + 150 ° C, but it is preferably -60 ° C to + 40 ° C in order to proceed the reaction with good yield.

The amount of the haloalkyl halide of the formula (VII) to be used is usually 0.9 to 3 mol, preferably 1 to 2 mol per 1 mol of bis (2-biphenyl) ditelluride. The reducing agent used in this step is
Although it depends on the type of the reducing agent, it is usually at least 0.5 mol with respect to 1 mol of bis (2-biphenyl) ditelluride in order to proceed the reaction with good yield, and bis (2-biphenyl) ditelluride is consumed. The amount required for this is appropriately selected.

[Step i-2] In this step, a halogen and a Bronsted acid (HX) or a Lewis acid (X ′) is reacted with the (haloalkyl) tellurobiphenyl of the formula (II) to give a compound of the formula (II) I-1) is for producing a (haloalkyl) dibenzotelurophenium salt.

In the present production step, the compound of formula (II) may be reacted with halogen and then Bronsted acid (HX) or Lewis acid (X ') may be reacted, or the compound of formula (I
It is also possible to add Bronsted acid (HX) or Lewis acid (X ′) to the compound of I) and subsequently react with halogen.

Examples of the halogen used in this step include fluorine (F ₂ ), chlorine (Cl ₂ ), bromine (Br ₂ ), iodine (I ₂ ). In order to suppress the violent reaction, the fluorine used in this step is usually an inert gas, and the fluorine gas diluted so that the volume of the inert gas is within the range of 99% to 50% is used. Preferably. Examples of the inert gas used for dilution include nitrogen, helium, argon and the like.

The amount of halogen used is an equimolar amount or more, relative to the (haloalkyl) tellurobiphenyl of the formula (II), but an approximately equimolar amount is preferable for economical efficiency and suppression of side reactions.

Bronsted acid (H
Examples of X) include HF, HCl, HBr, and hydrogen halides of HI; methanesulfonic acid, ethanesulfonic acid, butanesulfonic acid, benzenesulfonic acid, nitrobenzenesulfonic acid, dinitrobenzenesulfonic acid, chlorobenzenesulfonic acid, toluenesulfonic acid. , Trifluoromethanesulfonic acid, trichloromethanesulfonic acid, difluoromethanesulfonic acid, trifluoroethanesulfonic acid, tetrafluoroethanesulfonic acid, perfluorobutanesulfonic acid, perfluorooctanesulfonic acid, 10-camphorsulfonic acid, 3-bromocamphor-8 -Sulfonic acid,
Sulfonic acids such as sulfuric acid, fluorosulfonic acid, chlorosulfonic acid; formic acid, acetic acid, propionic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, benzoic acid, chlorobenzoic acid, nitrobenzoic acid, dinitrobenzoic acid, etc. Carboxylic acid; HBF ₄ , HBCl ₄ , HBF ₃ Cl, HAlCl ₄ , HA
lCl ₃ F, HPF ₄ , HPF ₆ , HAsF ₄ , HAsF ₆ , HSbF ₆ , HSbCl ₅
F, an acid consisting of a Lewis acid such as HSbCl ₆ and hydrogen halide; HBPh ₄ ,

[Chemical 23] Acid such as boron; nitric acid; halogen acid such as perchloric acid, perbromic acid, periodic acid, hypochlorous acid and the like.

The Lewis acid (X ') used in this step
For example, boron trifluoride (BF ₃ ), antimony pentafluoride (SbF ₅ ), antimony pentachloride (SbCl ₅ ), arsenic pentafluoride (AsF ₅ ), boron trichloride (BCl ₃ ), aluminum chloride Lewis acids such as (AlCl ₃ ) and phosphorus pentafluoride (PF ₅ ) can be mentioned.

The amount of the above Bronsted acid or Lewis acid used is at least an equimolar amount or more with respect to the (haloalkyl) tellurobiphenyl represented by the above formula (II) in order to promote the present reaction in good yield. However, it is preferable to use an approximately equimolar amount for economic reasons.

In the present reaction, when the Bronsted acid or Lewis acid used is a liquid, an excess amount thereof may serve as a solvent. However, a halogen-based organic solvent is usually used because of economical efficiency and easy post-treatment. It is preferable to use, for example, trichlorofluoromethane, trichlorotrifluoromethane, dichlorotrifluoromethane, methylene chloride, carbon tetrachloride,
Solvents such as chloroform, dichloroethane, trichloroethane, tetrachloroethane and trifluoroacetic anhydride are preferred.

The reaction temperature can be selected in the range of about -100 ° C to about + 200 ° C, and is preferably in the range of -85 ° C to + 150 ° C from the viewpoint of good yield and selectivity.

The (haloalkyl) tellurobiphenyl of the formula (II) and the (haloalkyl) dibenzotellophenium salt of the formula (I-1) thus obtained can be obtained by a method known per se, for example, a method such as crystallization or chromatography. It can be isolated and purified.

In the general formula (I-1), X = OS
When it is O ₂ R ⁵ , it can also be produced according to the following reaction formula ii.

Reaction formula ii

[Chemical 24] [In the above formula, Rf is the same as described above, R ³ and R ⁴ are each an alkyl group or an aryl group, and
⁵ represents a halogen-substituted or unsubstituted alkyl group or aryl group, and R ⁶ represents R ⁷ CO— or R ⁷ SO ₂ — (R ⁷ represents a halogen-substituted or unsubstituted alkyl group or aryl group). Is a group that is ]

[Step ii] In this step, the (haloalkyl) tellurobiphenyl of the formula (II) is reacted with the sulfoxide of the formula (III) and the sulfonic acid derivative of the formula (IV) to give the compound of the formula (I- 2) to produce (haloalkyl) dibenzotellophenium sulfonate.

The sulfoxide of the formula (III) is a compound which is industrially easily available, and examples thereof include dimethyl sulfoxide, diethyl sulfoxide, tetramethylene sulfoxide, diphenyl sulfoxide, phenylmethyl sulfoxide, di (chlorophenyl) sulfoxide and the like. be able to.

The sulfonic acid derivative of the above formula (IV) is a compound that is industrially easily available, and is, for example, methanesulfonic anhydride, trifluoromethanesulfonic anhydride, trichloromethanesulfonic anhydride, nonafluorobutanesulfone. Acid anhydride, benzenesulfonic acid anhydride, toluenesulfonic acid anhydride, nitrobenzenesulfonic acid anhydride,
Examples thereof include dinitrobenzenesulfonic anhydride, acetyltrifluoromethanesulfonate, trifluoroacetyltrifluoromethanesulfonate, trifluoroacetylnonafluorobutanesulfonate, and the like.

The amounts of the sulfoxide of the formula (III) and the sulfonic acid derivative of the formula (IV) used are at least equimolar or more with respect to the compound of the formula (II) in order to promote the reaction in good yield. However, it is preferable to use approximately equimolar amounts from the economical viewpoint.

This reaction is usually preferably carried out in a solvent, and examples of the solvent used include methylene chloride, chloroform, carbon tetrachloride, trichlorotrifluoroethane and the like.

The reaction temperature is usually about -80 ° C to about + 150 ° C.
However, in order to proceed the reaction with good yield, a temperature within the range of -50 ° C to + 100 ° C is preferable.

In the compound represented by the general formula (I), when either one or both of R ¹ and R ² is a nitro group, it can be produced according to the following reaction formula iv.

Reaction formula iii

[Chemical 25]

[Step iii] This step is the above-mentioned step i-2 or i
The nitrated (haloalkyl) of formula (I-3) is obtained by nitrating the (haloalkyl) dibenzotellofenium salt of formula (I-1) obtained in step i.
It is intended to produce a dibenzotellophenium salt.

In carrying out the nitration reaction in this step, it is not always necessary to use a solvent, but in order to proceed the reaction efficiently, generally, for example, nitromethane,
It is preferable to carry out the reaction in a solvent such as tetramethylene sulfone, trifluoromethanesulfonic acid or trifluoroacetic acid.

Examples of the reagent used in the nitration reaction include nitronium trifluoromethanesulfonate,
Nitronium tetrafluoroborate, nitronium hexafluorophosphate, nitric acid-sulfuric acid mixture, nitric acid-
Examples thereof include trifluoromethanesulfonic acid mixture.

In particular, the general formula (V):

[Chemical 26]

The amount of the reagent used in the above nitration reaction varies depending on the number of nitro groups to be introduced. For example, when one nitro group is introduced, the substantial nitrating reagent is represented by the formula (I- It is preferably used within a range of 1 to 1.5 equivalents relative to 1 mol of the compound of 1), and when two nitro groups are introduced, it is 2 per mol of the compound of formula (I-1). It is preferably used within the range of to 4 equivalents.

The temperature of the nitration reaction depends on the reactivity of both the reagent used and the compound of the formula (I-1) as a raw material, but it is generally about -20 ° C to + 100 ° C. Temperatures within the range are suitable.

The nitrated (haloalkyl) dibenzotellophenium of formula (I-3) obtained in the above step can be isolated and purified by a method known per se, for example, a method such as crystallization.

The (haloalkyl) dibenzotellophenium salt represented by the general formula (I) has the following reaction formula
It can also be prepared according to iv from other (haloalkyl) dibenzotelurophenium salts.

Reaction formula iV

[Chemical 27]

[Iv step] This step is the above-mentioned i-2 step, ii
Formulas (I-1) and (I-2) obtained in Step or Step iii
Alternatively, the (haloalkyl) dibenzotellophenium salt of (I-3) is used. In the present step, this is represented by the formula (I
-4) by reacting with a Bronsted acid salt represented by the above formula (VI) as a (haloalkyl) dibenzotelurophenium salt to cause a salt exchange reaction,
The present invention is for producing a (haloalkyl) dibenzotelurophenium salt represented by the formula (I).

Examples of the Bronsted acid salt used in this step include metal salts, ammonium salts and phosphonium salts of Bronsted acid.

As the Bronsted acid, the above-mentioned Bronsted acid (HX) can be mentioned. As a specific example of the metal atom of the metal salt, lithium,
Examples thereof include sodium, potassium, magnesium, calcium, mercury, silver and the like. Further, specific examples of the ammonium group of the ammonium salt include ammonium, monomethylammonium, dimethylammonium, trimethylammonium, tetramethylammonium, tetraethylammonium, tetrabutylammonium, benzyltrimethylammonium, pyridinium, N-methylpyridinium, quinolinium and the like. be able to. Moreover, specific examples of the phosphonium group of the phosphonium salt include tetramethylphosphonium, tetrabutylphosphonium, and tetraphenylphosphonium.

[0055]

[Chemical 28] In order to proceed this reaction in good yield, the amount is equimolar or more with respect to the compound of the formula (I-4), but from an economical point of view,
It is preferable to use an approximately equimolar amount to 5 times the molar amount.

In this reaction, it is usually preferable to use a solvent, for example, acetonitrile, propionitrile, diethyl ether, tetrahydrofuran, dimethylformamide, dimethylsulfoxide, methanol, ethanol, propanol, water, etc., or a mixed solvent thereof, etc. Can be illustrated.

The reaction temperature can be selected within the range of -20 ° C to + 150 ° C, but a temperature within the range of room temperature to 100 ° C is preferable in order to proceed the reaction with good yield.

[0058]

EXAMPLES The present invention will be described in more detail below with reference to examples and reference examples.

Example 1

[Chemical 29]

Under an argon atmosphere, sodium borohydride (476 mg) was added to a solution of 3.36 g (6 mmol) of bis (2-biphenyl) ditelluride in 45 ml of tetrahydrofuran (THF).
After adding (12.6 mmol), methanol 1.
02 ml (25.2 mmol) was added dropwise at such a rate that hydrogen was slowly generated. After stirring at room temperature for 30 minutes, the reaction mixture was cooled to -78
After cooling to 0 ° C., about 20 mmol of trifluoromethyl iodide were condensed in and added.

The reaction solution was warmed to room temperature over 3 hours and further stirred for 12 hours. Water was added to the reaction solution, followed by extraction with diethyl ether. The organic layer was washed with water and then with saturated saline, and dried over anhydrous magnesium sulfate. After the desiccant was filtered off, the filtrate was evaporated under reduced pressure.

4.59 g of the obtained brown oily substance was subjected to column chromatography on silica gel (developing solvent: ethyl acetate-
It was purified by hexane) to obtain 3.52 g (yield 84%) of 2-[(trifluoromethyl) telluro] biphenyl as an oily substance. Physical properties and spectral data of this product are shown below.

Bp 138.5 ° C. (6 mmHg) ¹⁹ F-NMR (internal standard CFCl ₃ ) (in CDCl ₃ ): 26.2 ppm (s,
CF ₃ )

¹ H-NMR (in CDCl ₃ ): 7.18 to 7.64 ppm (8 H,
m) 8.25ppm (1H, d, J = 8Hz, 3-H) IR (neat): 3058, 1460, 1082, 1006, 707, 702cm ^-1

Mass (m / e): 352, 350, 348, 347, 346
(M ⁺ ) Elemental analysis: Actual value: C, 44.56; H, 2.48% Calculated value: C, 44.64; H, 2.59%

Example 2

[Chemical 30]

Bis (2-biphenyl) ditelluride 3.36 was prepared in the same manner as in Example 1 except that trifluoromethyl bromide was used instead of trifluoromethyl iodide and the reaction time at room temperature was extended to 2 days. From g (6 mmol), 2
-[(Trifluoromethyl) telluro] biphenyl 2.93g
(Yield 70%) was obtained. The physical properties and spectral data of the product were the same as those shown in Example 1.

Example 3

[Chemical 31]

Under an argon atmosphere, 2-[(trifluoromethyl) telluro] biphenyl 700 mg (2 mmol) of 1,1,
Bromine 103 μl (2 mmol) was added dropwise to a solution of 2-trichloroethane (4 ml), and the mixture was stirred at room temperature for 40 minutes. Then, after adding 177 μl (2 mmol) of trifluoromethanesulfonic acid,
The mixture was stirred for 1 minute and then heated under reflux for 12 hours.

After allowing to cool, acetonitrile was added to the reaction solution, insoluble materials were removed by filtration, the filtrate was concentrated under reduced pressure, and the residue was thoroughly washed with diethyl ether to give Te- (trifluoromethyl) dibenzo. Tellurophenium trifluoromethanesulfonate (630 mg, yield 63%) was obtained as crystals. Purification was carried out by recrystallisation with acetonitrile-diethyl ether. Physical properties and spectral data of this product are shown below.

Decomposition point 212 ° C. ¹⁹ F-NMR (internal standard CFCl ₃ ) (in CD ₃ CN): 41.0 ppm (3F,
s, TeCF ₃ ) 78.0ppm (3F, s, CF ₃ )

¹ H-NMR (in CD ₃ CN): 7.75 ppm (2 H, td,
J = 7.6, 1.3Hz, 2,8 or 3,7-H) 7.86ppm (2H, td, J = 7.6, 1.3Hz, 2,8 or 3,7-H) 8.23 to 8.10ppm (4H, m, 1,4,6,9-H) IR (KBr): 1442, 1252, 1123, 1080, 1034, 751, 650cm
^-1

Mass (FAB method): 351, 349, 347, 346
(M ⁺ -OSO ₂ CF ₃ ) Elemental analysis: Actual value: C, 33.72; H, 1.52% Calculated value: C, 33.77; H, 1.62%

Example 4

[Chemical 32]

Under an argon atmosphere, a solution of 2-[(trifluoromethyl) tello] biphenyl 10.5 g (30 mmol) in methylene chloride 30 ml was added with dimethyl sulfoxide 2.1 ml (30 mmo).
l) was added, the mixture was cooled with ice, and 5.5 ml (33 mmol) of trifluoromethanesulfonic anhydride was slowly added dropwise with stirring.

After stirring at room temperature for 1 hour, diethyl ether was added to the reaction solution to completely precipitate crystals. The crystals were collected by filtration and washed thoroughly with diethyl ether. The obtained crystals were purified by recrystallization from acetonitrile-diethyl ether to give Te- (trifluoromethyl) dibenzotellophenium trifluoromethanesulfonate 1
2.6 g (yield 84%) was obtained. The physical properties and spectral data of the product were the same as those shown in Example 3.

Example 5

[Chemical 33]

Under an argon atmosphere, 252 μl (6 mmol) of fuming nitric acid (d = 1.50) and 1.22 ml (7.3 mmol) of trifluoromethanesulfonic anhydride were added to a reaction vessel, and the mixture was stirred at room temperature for 40 minutes to give nitronium trifluoromethane. A sulfonate was prepared. To this was added 1.0 g (2 mmol) of Te- (trifluoromethyl) dibenzotellophenium trifluoromethanesulfonate, which had been ground into a powder form, and further 1
Stir for hours.

Under cooling with ice, diethyl ether was foamed in this reaction solution and slowly added while paying attention to heat generation to precipitate crystals, which were collected by filtration, thoroughly washed with diethyl ether, and dried to give 3,7. 900 mg (yield 76%) of -dinitro-Te- (trifluoromethyl) dibenzotellophenium trifluoromethanesulfonate was obtained. Purification was performed by recrystallization from acetonitrile-diethyl ether. Physical properties and spectral data of the product are shown below.

Decomposition point 275-280 ° C. ¹⁹ F-NMR (internal standard CFCl ₃ ) (in CD ₃ CN): 39.3 ppm (3F, 3F,
s, TeCF ₃ ) 78.0ppm (3F, s, CF ₃ )

¹ H-NMR (in CD ₃ CN): 8.50 ppm (2 H, d, J
= 8.7Hz, 1,9-H) 8.68ppm (2H, dd, J = 8.7, 2.2Hz, 2,8-H) 9.50ppm (2H, d, J = 2.2Hz, 4,6-H) IR ( KBr): 1595, 1527, 1344, 1256, 1170, 1067, 102
3, 862,738, 636cm ^-1

Mass (FAB method): 441, 439, 437 (M ⁺
-OSO ₂ CF ₃ ) Elemental analysis: Actual value: C, 28.65; H, 1.05; N, 4.54% Calculated value: C, 28.60; H, 1.03; N, 4.77%

Example 6

[Chemical 34]

Under an argon atmosphere, Te- (trifluoromethyl) dibenzotellophenium trifluoromethanesulfonate (498 mg, 1 mmol) in acetonitrile (4 ml) was added,
A solution of 332 mg (1 mmol) of tetrabutylammonium bromide in 1 ml of acetonitrile was slowly added dropwise at room temperature, and the mixture was stirred for 3.5 hours.

The white crystals thus formed were collected by filtration, sufficiently washed with acetonitrile and subsequently with diethyl ether, and then dried to obtain 350 mg (yield 82%) of Te- (trifluoromethyl) dibenzotellophenium bromide. Purification was performed by recrystallization from methanol-hexane. Physical properties and spectral data of the product are shown below.

Decomposition point 245 ° C. ¹⁹ F-NMR (internal standard CFCl ₃ ) (CD ₃ CN + DMSO-d ₆ (8: 2)
Medium): 45.0ppm (s, CF ₃ )

¹ H-NMR (CD ₃ CN + DMSO-d ₆ (8: 2)
Medium): 7.58ppm (2H, td, J = 7.6, 1.3Hz, 2,8 or 3,
7-H) 7.73ppm (2H, td, J = 7.6, 1.3Hz, 2,8 or 3,7-H) 8.
11ppm (2H, dd, J = 7.6, 1.3Hz, 1,9-H) 8.34ppm (2H, dd, J = 7.6, 1.3Hz, 4,6-H) IR (KBr): 1442, 1124, 1079, 750 cm ^-1

Mass (FAB method): 351, 349, 347 (M ⁺
-Br) Elemental analysis: Found: C, 36.68; H, 1.72% Calculated: C, 36.42; H, 1.88%

Example 7

[Chemical 35]

A mixture of 200 mg (0.467 mmol) of Te- (trifluoromethyl) dibenzotellophenium bromide, 91 mg (0.467 mmol) of silver tetrafluoroborate, and 2 ml of anhydrous acetonitrile was refluxed for 25.5 hours. After the insoluble matter was filtered off, the solvent was distilled off.

The obtained crystalline solid was thoroughly washed with methylene chloride to obtain 180 mg of Te- (trifluoromethyl) dibenzotellophenium tetrafluoroborate (yield 89%). Purification was performed by recrystallization from acetonitrile-diethyl ether. Physical property values and spectrum data are shown below.

Decomposition point 219 to 220 ° C. ¹⁹ F-NMR (internal standard CFCl ₃ ) (in CD ₃ CN): 40.4 ppm (3F, 3F,
s, TeCF ₃ ) 149.4ppm (4H, s, BF ₄ )

¹ H-NMR (in CD ₃ CN): 7.72 ppm (2H, td,
J = 7.6, 1.4Hz, 2,8 or 3,7-H) 7.89ppm (2H, td, J
= 7.6, 1.3Hz, 2,8 or 3,7-H) 8.17 to 8.23ppm (4H, m, 1,4,6,9-H) IR (KBr): 3058, 1443, 1167, 1060, 1024, 754, 519,
472 cm ^-1

Mass (FAB method): 351, 349, 347 (M ⁺
-BF ₄ ) Elemental analysis: Actual value: C, 35.75; H, 1.67% Calculated value: C, 35.84; H, 1.85%

Next, reference examples using the compound according to the present invention as a trifluoromethylating agent will be described. Reference example 1

[Chemical 36]

Under an argon atmosphere, a solution of 74 mg (0.65 mmol) of 2-methylcyclopenta-1,3-dione in 1.5 ml of DMF was added with sodium hydride (60% in o
il) 26 mg (0.65 mmol) was added, and the mixture was stirred at room temperature for 15 minutes. After ice-cooling again, 3,7-dinitro-Te- (trifluoromethyl) dibenzotellophenium trifluoromethanesulfonate (294 mg, 0.5 mmol) was added, and the mixture was stirred under ice-cooling for 0.5 hours and further at room temperature for 1 hour. did.

By quantifying this reaction solution by ¹⁹ F-NMR, it was found that 2-trifluoromethyl-2-methylcyclopenta-1,3-dione was produced in a yield of 55%. Then, the reaction solution was post-treated in a usual manner to obtain the product 2-trifluoromethyl-2-methylcyclopenta-1,3-dione as a volatile oil. The physical properties and spectral data of the product are shown below.

¹⁹ F-NMR (internal standard CFCl ₃ ) (in CDCl ₃ ): 6
^{_{9.8ppm (s, CF 3) 1}} H-NMR ( in _{CDCl 3): 1.38ppm (3H,} s, CH 3) 2.68~3.15ppm (4H, m, (CH 2) 2)

IR (neat): 1740 cm ^-1 (CO) Mass (m / e): 180 (M ⁺ ) Elemental analysis: Actual value: C, 46.86; H, 3.89% Calculated value: C, 46.68; H, 3.92 %

Reference Example 2

[Chemical 37]

In a reaction vessel, 3,7-dinitro-Te- (trifluoromethyl) dibenzotellophenium trifluoromethanesulfonate 147 mg (0.25 mmol) DMF 0.6 ml
After adding the solution and adding 46 μl (0.5 mmol) of aniline, 80 ℃
In an oil bath for 18 hours. When the reaction solution was quantified by ¹⁹ F-NMR spectrum, 0.11 mmol of o- (trifluoromethyl) aniline (yield 44%) and 0.053 mmol of p- (trifluoromethyl) aniline (yield 21%) were produced. Was. The structure of the product was confirmed by comparing the spectrum with a standard sample.

Example 8

[Chemical 38]

Under an argon atmosphere, a solution of bis (2-biphenyl) ditelluride (2.8 g, 5 mmol) in THF (35 ml) was added,
After adding 420 mg (10 mmol) of sodium borohydride,
While stirring under ice cooling, 810 μl (20 mmol) of methanol was slowly added dropwise. After stirring at room temperature for 30 minutes, the reaction solution was cooled to −78 ° C. and n-heptafluoropropyl iodide was added.
While adding 4.3 ml (30 mmol) and stirring, the temperature was raised to room temperature over about 2 hours, and the mixture was further stirred at room temperature overnight.

Water was added to the reaction solution, which was then extracted with diethyl ether. The organic layer was washed with water and then with saturated saline, and dried over anhydrous magnesium sulfate. After the desiccant was filtered off, the solvent of the filtrate was distilled off under reduced pressure.

5.4 g of the obtained brown oily substance was purified by column chromatography on silica gel (developing solvent; n-hexane) to obtain 4.2 g (92%) of 2-[(n-heptafluoropropyl) telluro] biphenyl. Obtained. Physical properties and spectral data of this product are shown below.

Melting point: 36 to 37 ° C. ¹⁹ F-NMR (internal standard CFCl ₃ ) (in CDCl ₃ ): 79.6 ppm (3 F,
t, J = 9Hz, CF ₃ ), 86.3 (2F, m, TeCF ₃ ), 120.1 (2F, t, J
= 4Hz, CF ₂ )

¹ H-NMR (in CDCl ₃ ): 7.18 to 7.49 ppm (8 H,
m), 8.11 (1H, d, J = 8Hz, 3-H) IR (KBr): 1686, 1459, 1327, 1222, 1187,1106, 812,
754, 728cm ^-1

Mass (m / e) (FAB method): 452, 450, 448, 44
7,446, 445, 443 (M ⁺ ) Elemental analysis: Actual value: C, 39.93; H, 1.83% Calculated value: C, 40.05; H, 2.02%

Example 9

[Chemical 39]

Instead of n-heptafluoropropyl iodide, 13.6 g of n-heptadecafluorooctyl iodide
The reaction and post-treatment were carried out under the amounts and amounts of the solvent and reagents shown in Example 8 and the reaction conditions and operations except that (25 mmol) was used. Fluorooctyl) telluro] biphenyl was obtained as crystals. Physical properties and spectral data of this product are shown below.

Melting point: 51 ° C. ¹⁹ F-NMR (internal standard CFCl ₃ ) (in CDCl ₃ ): 81.1 ppm (3 F,
t, J = 10Hz, CF ₃ ), 85.0 (2F, m, CF ₂ ), 115.5 (2F, m, CF
₂ ), 121.5 (2F, m, CF ₂ ), 122.1 (4F, m, 2xCF ₂ ), 122.9 (2
F, m, CF ₂ ), 126.3 (2F, m, CF ₂ )

¹ H-NMR (in CDCl ₃ ): 7.19 to 7.50 ppm (8 H,
m), 8.12 (1H, d, J = 8Hz, 3-H) IR (KBr): 1370, 1244, 1204, 1147, 1083,919, 761, 6
99, 645, 556cm ^-1

Mass (m / e) (FAB method): 702, 700, 698, 69
7,696, 695, 694 (M ⁺ ) Elemental analysis: Actual value: C, 33.98; H, 1.23% Calculated value: C, 34.32; H, 1.30%

Example 10

[Chemical 40]

2-[(n-heptafluoropropyl) telluro] biphenyl 450 mg (1 mmol) and dimethylsulfoxide 71 μl (1 mmol) in a solution of 4 ml of THF under ice cooling, trifluoromethanesulfonic anhydride 185 μl (1.1 mmol)
Was slowly added dropwise. The mixture was stirred under ice cooling for 1 hour and further at about 7 ° C. for 2 hours.

Then, diethyl ether was added to the reaction solution, and the precipitated white crystals were collected by filtration. The obtained crystals were recrystallized from acetonitrile-diethyl ether to obtain 444 mg (74%) of Te- (n-heptafluoropropyl) dibenzotellophenium trifluoromethanesulfonate as white crystals. Physical properties and spectral data of this product are shown below.

Decomposition point: 162 ° C. ¹⁹ F-NMR (internal standard CFCl ₃ ) (in CD ₃ CN): 77.9 ppm (3 F,
s, SO ₂ CF ₃ ), 79.1 (3F, t, J = 9Hz, CF ₃ ), 96.0 (2F, q, J =
9Hz, CF ₂ ), 119.1 (2F, s, CF ₂ )

¹ H-NMR (in CD ₃ CN): 7.73 ppm (2 H, td, J
= 12, 2Hz), 7.90 (2H, td, J = 12, 2Hz), 8.17 (2H, d.
m, J = 12Hz), 8.22 (2H, dd, J = 12, 2Hz) IR (KBr): 1444, 1278, 1223, 1129, 1025,750cm ^-1

Mass (m / e) (FAB method): 451, 449, 447, 44
6,445, 444, 443 (M ⁺ -OSO ₂ CF ₃ ) Elemental analysis: Actual value: C, 32.22; H, 1.28% Calculated value: C, 32.14; H, 1.35%

Example 11

[Chemical 41]

202 mg (1 mmol) of diphenyl sulfoxide was added to a solution of 450 mg (1 mmol) of 2-[(n-heptafluoropropyl) telluro] biphenyl in 4 ml of THF. While stirring at room temperature, 185 μl (1.1 mmol) of trifluoromethanesulfonic anhydride was slowly added thereto, and the mixture was stirred for 2 hours.

Diethyl ether was added to the reaction solution, and the precipitated crystals were collected by filtration to obtain 454 mg (76%) of Te- (n-heptafluoropropyl) dibenzotellophenium trifluoromethanesulfonate. Further, for purification, recrystallization was performed from acetonitrile-diethyl ether. The physical properties and spectrum data of the obtained crystal were identical to those obtained in Example 10.

Example 12

[Chemical 42]

Instead of 2-[(n-heptafluoropropyl) telluro] biphenyl, 700 mg (1 mm of 2-[(n-heptadecafluorooctyl) tello] biphenyl was used.
ol), except that the amount of the solvent and the reagents shown in Example 10 and the reaction conditions and operations were the same as those in Example 10 to carry out the reaction and post-treatment to give 559 mg
(66%) Te- (n-heptadecafluorooctyl) dibenzotellophenium trifluoromethanesulfonate was obtained as white crystals. The physical properties and spectral data of this product are shown below.

Melting point: 172-173 ° C. (with decomposition) ¹⁹ F-NMR (internal standard CFCl ₃ ) (in CD ₃ CN): 78 ppm (3 F, s,
SO ₂ CF ₃ ), 80 (3F, t, J = 10Hz, CF ₃ ), 95 (2F, m, CF ₂ ), 11
4 (2F, m, CF ₂ ), 121 (6F, m, 3xCF ₂ ) 122 (2F, m, CF ₂ ), 125 (2F, m, CF ₂ )

¹ H-NMR (in CD ₃ CN): 7.74 ppm (2 H, td, J
= 7.8, 1.3Hz), 7.91 (2H, td, J = 7.8, 1.3Hz), 8.15 (2H,
dm, J = 7.8Hz), 8.23 (2H, dd, J = 7.8, 1.3Hz) IR (KBr): 1444, 1281, 1240, 1221, 1151,1023, 752,
634 cm ^-1

Mass (m / e) (FAB method): 701, 699, 697, 69
6,695, 694, 693 (M ⁺ -OSO ₂ CF ₃ ) Elemental analysis: Actual value: C, 29.42; H, 0.79% Calculated value: C, 29.75; H, 0.95%

[0128]

According to the present invention, the above-mentioned (haloalkyl) dibenzotellophenium salt of the general formula (I) has a novel structure in which a haloalkyl group which is an electron-withdrawing group is bonded to a tellurium atom of a dibenzotellophenium skeleton. The electron density of the tellurium atom is reduced due to the organic tellurium structure, and by converting R ¹ and R ² on the 6-membered ring from a hydrogen atom to an electron-withdrawing group such as a nitro group, The electron density of atoms can be further reduced. Therefore, it has a novel structure characteristic of the present invention (haloalkyl)
The dibenzotellophenium salt becomes useful as a new reagent for organic synthesis and as a new organic material.

Claims (7)

[Claims] 1. General formula (I): A (haloalkyl) dibenzotellophenium salt represented by: 2. General formula (II): (In this general formula, Rf is a haloalkyl group having 1 to 10 carbon atoms.) A production intermediate comprising (haloalkyl) tellurobiphenyl. 3. General formula (II): (In this general formula, Rf is a haloalkyl group having 1 to 10 carbon atoms.) A (haloalkyl) tellurobiphenyl is reacted with halogen and Bronsted acid (HX) or Lewis acid (X '). General formula (I-1): embedded image A method for producing a (haloalkyl) dibenzotellophenium salt represented by: 4. General formula (II): (In this general formula, Rf is a haloalkyl group having 1 to 10 carbon atoms.) A (haloalkyl) tellurobiphenyl represented by the general formula (III): (In this general formula, R ³ and R ⁴ are each an alkyl group or an aryl group.) And a general formula (IV): embedded image R ⁵ SO ₂ OR ⁶ [in the general formula , R ⁵ is a halogen-substituted or unsubstituted alkyl group or aryl group, and R ⁶ is R ⁷ CO— or R ^7.
7 SO ₂ — (R ⁷ is a halogen-substituted or unsubstituted alkyl group or aryl group.). ] The compound represented by the general formula (I-2): (In this general formula, Rf and R ⁵ are the same as those described above.) Represented by (haloalkyl) METHOD dibenzo tellurocarbonyl Fe iodonium sulfonates. 5. General formula (I): And a (haloalkyl) dibenzotellophenium salt represented by the following general formula (V): XNO ₂ (wherein X is the same group as the conjugate base of the Bronsted acid). A compound of the general formula (I-3): A method for producing a nitrated (haloalkyl) dibenzotellophenium salt represented by: 6. General formula (I-4): A (haloalkyl) dibenzotellophenium salt represented by the general formula (VI): Reacting with a Bronsted acid salt represented by the general formula (I): A method for producing a (haloalkyl) dibenzotellophenium salt represented by: 7. Structural formula (I): embedded image Bis (2-biphenyl) ditelluride represented by the formula, a reducing agent, and general formula (VII): embedded image Rf—Y (wherein Rf is a haloalkyl group having 1 to 10 carbon atoms, Y is a halogen atom.) Is reacted with a haloalkyl halide represented by
General formula (II): (In this general formula, Rf is the same as described above.)
A method for producing (haloalkyl) tellurobiphenyl represented by: