COMPOSITION, FLUORINATING REAGENT, AND METHOD FOR PRODUCING FLUORINATED ORGANIC COMPOUND

Abstract

An object of the present invention is to provide a method for producing a fluorinated organic compound with a high yield without using carbon tetrachloride in view of the fact that the production of a fluorinated organic compound with a sufficient yield was impossible for a hitherto-known method that uses a fluorinating agent that contains IF.sub.5-pyridine-HF alone. Another object of the present invention is to provide a fluorinating reagent that is capable of achieving this object. The present invention provides a composition comprising (1) IF.sub.5 and (2) an aprotic solvent (with the proviso that carbon tetrachloride is excluded), wherein the aprotic solvent is contained in an amount within a range of 50 mass ppm to 20 mass %.

Claims

1. A composition comprising: (1) IF.sub.5 and (2) at least one aprotic solvent selected from the group consisting of (cyclo)alkanes, chlorine-containing organic solvents, with the proviso that carbon tetrachloride is excluded, aromatic solvents, nitrile-containing organic solvents, and fluorine-containing organic solvents, wherein the aprotic solvent is contained in an amount within a range of 50 mass ppm to 20 mass %.

2. The composition according to claim 1, further comprising an acid and a base.

3. The composition according to claim 1, further comprising HF and an organic base.

4. The composition according to claim 1, the composition comprising: (1) IFs-pyridine-HF and (2) at least one aprotic solvent selected from the group consisting of (cyclo)alkanes, chlorine-containing organic solvents, with the proviso that carbon tetrachloride is excluded, aromatic solvents, nitrile-containing organic solvents, and fluorine-containing organic solvents, wherein the aprotic solvent is contained in an amount within a range of 50 mass ppm to 20 mass %.

5. The composition according to claim 1, wherein the aprotic solvent is at least one member selected from the group consisting of C.sub.1-10 (cyclo)alkanes, C.sub.1 or C.sub.2 chlorine-containing organic solvents, and C.sub.1-7 fluorine-containing organic solvents.

6. The composition according to claim 1, wherein the aprotic solvent is a C.sub.1-10 (cyclo)alkane.

7. The composition according to claim 1, wherein the aprotic solvent is cyclohexane.

8. The composition according to claim 1, which is a fluorinating reagent.

9. A method for producing a fluorinated organic compound, the method comprising Step A of fluorinating an organic compound by bringing the organic compound into contact with the composition of claim 1.

Description

EXAMPLES

[0235] The present invention is described below in further detail. However, the present invention is not limited to these Examples.

[0236] In the Examples, the unit ppm refers to mass ppm, unless otherwise specified.

[0237] The following is the meaning of the symbol used in the Examples. [0238] pen: Pentyl

[0239] In each Example, the amount of cyclohexane residue was measured according to the following measurement method.

Measurement Method

[0240] i) Accurately weigh about 50 to 150 mg of a sample composition; [0241] ii) Add 4 ml of 0.1 N KOH aqueous solution; [0242] iii) Add 2 ml of toluene; [0243] iv) Stir the mixture for 5 minutes, and allow the resulting mixture to stand for 10 minutes; [0244] v) Subject the cyclohexane residue in the toluene layer to GC measurement; and [0245] vi) Calculate the amount of cyclohexane residue, based on the calibration curve value. The average value obtained with n=3 is considered the amount of cyclohexane residue. The amount of cyclohexane residue as used herein means the amount of cyclohexane contained in the sample composition, i.e., (mass of cyclohexane)/(mass of the sample composition).

Production Example 1

[0246] IF.sub.5 (45 g, 0.20 mol) was placed in a container, to which 200 ml of cyclohexane was added at 0 C., followed by further addition of pyridine-HF (pyridine 50 mol %, HF 50 mol %) (20 g, 0.20 mol each). The resulting mixture was stirred for 30 minutes at 0 C., and then left to stand at room temperature for 1 hour to thus obtain a solid. containing IF.sub.5-pyridine-HF and cyclohexane.

[0247] The obtained solid was dried under reduced pressure while varying the conditions for drying under pressure. In this manner, solid compositions containing IF.sub.5-pyridine-HF and cyclohexane were obtained with various cyclohexane amounts. Hereinafter, these solid compositions are referred to as IF.sub.5-pyridine-HF, and its cyclohexane content is referred to as the amount of cyclohexane residue.

Example 1

Fluorination Reaction Test

[0248] ##STR00009##

[0249] 1F.sub.5-pyridine-HF (1.1 mmol) (the amount of cyclohexane residue: 202 mass ppm) and dichloromethane (2.0 mL) were placed in a reactor with a lid, to which substrate 1 (1.0 mmol) was added, and the mixture was allowed to react at 0 C. for 3 hours.

[0250] After purification, an internal standard (hexafluorobenzene) was added to the residue, and the product was quantified by .sup.19F-NMR. The results indicate that difluoro body 2 was produced with a yield of 60%.

Comparative Example 1

Fluorination Reaction Test

[0251] IF.sub.5-pyridine-HF (1.1 mmol) (the amount of cyclohexane residue: 43 mass ppm) and dichloromethane (2.0 mL) were placed in a reactor with a lid, to which substrate 1 (1.0 mmol) was added at room temperature, and the mixture was allowed to react at 0 C. for 3 hours. After purification, an internal standard (hexafluorobenzene) was added to the residue, and the product was quantified by .sup.19F-NMR. As a result, difluoro body 2 was not detected, and the yield was 0%, indicating that difluoro body 2 was not produced.

Test Example 1

Fluorination Reaction Test

[0252] Table 1 shows the results of the fluorination reaction test performed with respect to the samples of each product produced as in Example 1 and Comparative Example 1, using IF.sub.5-pyridine-HF with various amounts of cyclohexane residue (Examples 1 to 4 and Comparative Examples 1 and 2). As is clear from the results, the use of the composition of the present invention allows the fluorination reaction to proceed to thus yield the target product.

TABLE-US-00001 TABLE 1 No. 1 2 3 4 5 6 (Ex. 2) (Ex. 1) (Ex. 3) (Ex. 4) (Comp. Ex. 1) (Comp. Ex. 2) Amount of 19 mass % 202 ppm 99 ppm 87 ppm 43 ppm 33 ppm cyclohexane residue Fluorination + + + + n.d. n.d. reaction +: The fluorinated reaction product (difluoro body 2) was detected. n.d.: The fluorinated reaction product (difluoro body 2) was not detected.